Is Mac Lane still the best place to learn category theory? For a student embarking on a study of algebraic topology, requiring a knowledge of basic category theory, with a long-term view toward higher/stable/derived category theory, ... 

Is Mac Lane still the best place to start?

Or has the day arrived when it is possible to directly learn ($\infty$,n)-categories, without first learning ordinary category theory?  (So the next generation will be, so to speak, natively derived.)  If so, via what route?  If not, what's the most efficient path through the classical core material to a modern perspective?
 A: I would start from "Sets for mathematics", and then going to MacLane.
A: I found the Catsters on YouTube divinely useful.
John Baez, in his not so weekly blog, inspiring.
The n-category cafe, to keep you going.
Eugenia Cheng's notes on category theory was tremendously useful.
Eventually, Mac Lane began to make sense, as did Borceux; but oh, ever so slowly.
Sets for mathematicians is pretty.
And the n-lab is a great resource, but mostly dazzles my eyes...
And yes, 1-category theory is definitely best to start with, and be familiar with; but keep an eye on the higher grounds too.
A: I'm a fan of Kashiwara and Schapira's "Categories and sheaves"... they do cover a lot of material ; you can see the table of contents here: http://books.google.com/books/about/Categories_and_sheaves.html?id=K-SjOw_2gXwC
A: I doubt that someone could learn higher category theory (and more in general higher dimensional algebra) without first studying a little of category theory, mostly because the definition given in such context use a lot of category theoretic machinery.
About the textbook reference: MacLane's "Category theory for working mathematicians" may be a little outdated but I think it is still one of the most complete book of basic category theory second just to Borceux's books. Anyway there isn't a best book to learn basic category theory, any person could find a book better than another one, so I suggest you to take a look a some of these books, then choose which one is the best for you:
S. MacLane: Category theory for working mathematicians (I've already said a lot about this)
S. Awodey: Category theory (Peculiar because it has very low prerequisites and it's rich of examples too) 
J. Adamek,H. Herrlich, G. Strecker: Abstract and concrete category theory (freely avaible at at this site "http://katmat.math.uni-bremen.de/acc/acc.pdf", maybe the book with the greatest number of examples from topology and algebra)
After you have read one of these book, you could also use Borceux's books and read some more advanced chapter of category theory which aren't discussed in the previous books.
F. Borceux: Handbook of Categorical Algebra 1: Basic Category Theory
F. Borceux: Handbook of Categorical Algebra 2: Categories and Structures
F. Borceux: Handbook of Categorical Algebra 3: Categories of Sheaves
For higher category theory I know just few reference: 
Leinster's "Higher Operads Higher Categories" (http://arxiv.org/abs/math/0305049), 
and 
Lurie's "Higher Topos Theory" (http://arxiv.org/abs/math/0608040) 
other good reference in higher category theory and higher dimensional algebra in general are Baez'This week's finds and arxiv articles Higher dimensional algebra*.
Hope this may help.
A: Best paper to get a feel for Category Theory is "When is one thing equal to some other thing" by Barry Mazur. The paper can be obtained at--
http://www.math.harvard.edu/~mazur/preprints/when_is_one.pdf
A: I recommend for a first reading on category theory:
Martin Brandenburg, Einführung in die Kategorientheorie
It is really an excellent exposition with some nice perspectives on the concepts,
supported by plenty of examples. :)
(Note that it is provided in German only.)
A lot of thanks to Konrad S. for suggesting to me the reference!
(Such a pity, that I just missed the chance to meet the author in person..)
A: I third what Mike wrote: "one definitely needs a solid grounding in 1-category theory before learning higher category theory". With that being said, elaborating and expounding upon janed0e's suggestion, what follows are two study plans according to the prior knowledge of the student. Of course, there is no canonical way to approach learning higher category theory, so adjust the readings as needed. Note well, following the modern terminology as developed by Joyal, quasicategories are a model for ($\infty$, 1)-categories. Following the modern terminology as developed by Lurie, the unqualified usage of '$\infty$-category' or '$\infty$-categories' designates '($\infty$, 1)-category' and '($\infty$, 1)-categories', respectively.
Assumption: Student has no knowledge of 1-category theory (or simplicial sets) and wishes to get the flavor of infinity-category theory, without getting bogged down by technical details, in as short a time as can be reasonably expected. The implicit assumption is that the student has a budget of zero dollars.
Possible reading material and sequence with which to read:
0) J. Adamek, H. Herrlich, G. Strecker: Abstract and Concrete Categories: The Joy of Cats
1) G. Friedman: An elementary illustrated introduction to simplicial sets
2) J. Lurie: What is ... an $\infty$-Category?
3) M. Boyarchenko: Notes and Exercises on $\infty$-categories
4) M. Groth: A Short Course on $\infty$-categories(http://www.math.ru.nl/~mgroth/preprints/groth_scinfinity.pdf)
Repeating what Giorgio Mossa wrote, (0) has an abundant number of examples from topology, algebra, and theoretical computer science. As Mike Shulman noted, (0) is rather idiosyncratic. (0) uses the term 'quasicategory' for what Mac Lane called metacategories.  See the nLab page metacategory (http://ncatlab.org/nlab/show/metacategory) for further clarification about the terminology clash. (0) can be supplemented with video lectures by the Catsters (http://www.scss.tcd.ie/Edsko.de.Vries/ct/catsters/linear.php) and Wikipedia's Outline of category theory (http://en.wikipedia.org/wiki/Outline_of_category_theory).
Assumption: Student has knowledge of 1-category theory (but not simplicial sets) and wishes to get an in depth experience of infinity-category theory, allowing an 'ample' amount of time.
Possible reading material and sequence with which to read:
0) P. G. Goerss and J. F. Jardine: Simplicial Homotopy Theory (http://dodo.pdmi.ras.ru/~topology/books/goerss-jardine.pdf)
1) J. Lurie: What is ... an $\infty$-Category?
   (http://www.ams.org/notices/200808/tx080800949p.pdf)
2) M. Boyarchenko: Notes and Exercises on $\infty$-categories (http://www.math.uchicago.edu/~mitya/langlands/quasicategories.pdf)
3) M. Groth: A Short Course on $\infty$-categories
(http://www.math.uni-bonn.de/~mgroth/InfinityCategories.pdf)
4) J. Lurie: On the Classification of Topological Field Theories 
 (http://arxiv.org/abs/0905.0465)
5) C. Simpson: Homotopy Theory of Higher Categories
(http://hal.archives-ouvertes.fr/docs/00/44/98/26/PDF/main.pdf)
6) J. Lurie: Higher Topos Theory
(http://www.math.harvard.edu/~lurie/papers/highertopoi.pdf)    
(4) may be a more readable than (6), since (4) is an expository paper that gives an 
informal account of the classification of topological field theories using the technology of 
($\infty$, n)-categories. (4) can be nicely supplemented by Lurie's video lecture series 
on "Topological Quantum Field Theories and the Cobordism Hypothesis"  (http://lab54.ma.utexas.edu:8080/video/lurie.html), as well as the corresponding
notes for said lecture  (http://www.ma.utexas.edu/users/plowrey/dev/rtg/notes/perspectives_TQFT_notes.html).
(5) offers a broad perspective of current research in higher category theory.
(6) develops in detail the vast generalization of 1-category theory to ($\infty$, 1)-category theory.
For further roadmaps on learning higher category theory, look at this nForum discussion on reading Lurie's Higher Topos Theory  (http://www.math.ntnu.no/~stacey/Mathforge/nForum/comments.php?DiscussionID=2748&page=1#Item_0).
Hope this helps.
A: I just reviewed what I firmly believe will be the book that will replace MacLane as The Gold Standard for introductions to category theory for graduate students: Category Theory in Context by Emily Riehl. It's developed over the last several years from courses in category theory that Riehl has taught at Harvard and John Hopkins University to strong undergraduates and first year graduate students. She posted her evolving notes at her website each time and the first time I saw a rough draft, I knew she was writing something special. The finished text did not disappoint. It's comprehensive, incredibly clear and amazingly rich in examples, including many you've probably never considered. It's a remarkable book and I think it's going to replace MacLane very quickly once it's known to most experts. Best of all, it's much cheaper then MacLane! 
If you're interested in category theory, this is the book you want to learn from. I wish it was the one I'd learned from. 
My full review can be found here. 
A: You may find this helpful:
"A Short Course on Infinity-Categories" by Moritz Groth
http://www.math.uni-bonn.de/~mgroth/InfinityCategories.pdf
You'll first need to learn homotopy theory.
Reference [GJ99](Simplicial Homotopy Theory) in the above link
could be a place to start.
