This question may not be as easy to answer as you think! Some tangentially-related questions have appeared on math.stackexchange but I'm not really convinced by the answers.
In the sequel I will assume all vector spaces under discussion are finite dimensional.
A vector space is naturally isomorphic to its double dual
In an early linear algebra course we are told that "a finite dimensional vector space is naturally isomorphic to its double dual". The isomorphism in question is ${**}_V : V \to V^{**}$, $v^{**}(\phi) = \phi(v)$. We are told that this isomorphism is "natural" because it doesn't depend on any arbitrary choices. The notion of "natural", or "independent or arbitrary choice", is made precise via the concept of a category theoretical "natural transformation". Specifically, the operation $**$ on vector spaces gives rise to a functor whose action on maps is $f^{**} : V^{**} \to W^{**}$, $f^{**}(v^{**}) = f(v)^{**}$. In fact this is exactly the condition for the naturality square to commute and so ${**}_V$ is indeed a natural transformation (between the identity functor and $**$) which is an isomorphism.
A vector space is naturally isomorphic to its dual!
So far, so familiar. But there's something that doesn't quite hold up about all this. Let's adapt the above to show that $V$ and $V^*$ are "naturally isomorphic". We do this by following exactly the same procedure, replacing $**$ everywhere with $*$. The only change we have to make is to come up with an arbitrary isomorphism $*_V$ for each $V$. Other than that, the whole construction goes through unchanged. Specifically, once we have chosen $*_V$ we define the functorial action on morphisms to be $f^{*} : V^{*} \to W^{*}$, $f^{*}(v^{*}) = f(v)^{*}$.
In particular I have a natural isomorphism between the identity functor and $*$!
Objections to the construction
One could make a few objections to this construction, but they seem to be circular.
"But you admitted that $*_V$ depends on an arbitrary choice!"
I did, but that was informal language. In what formal sense is it arbitrary? The notion of "naturality" was supposed to rule out constructions that are arbitrary!
"Your definition of $f^*$ is invalid. It depends on $*_V$."
So what? My definition of $f^{**}$ depends on ${**}_V$ but it is uncontroversial.
"You should have defined $f^{**}(\hat{v})(\phi) = \hat{v}(\phi \circ f)$ and then it's clear that it doesn't depend on $**_V$. You can't do that for $f^*$."
But your $f^{**}$ is the same as my $f^{**}$! Is there some formal way of specifying that a functor does not depend on a natural transformation? And besides, what's the problem if it does?
"It's a problem because it depends on something that depends on arbitrary choice ..."
"Whilst the functor $**$ is the real double dual functor, $*$ is one you just made up. It is indeed isomorphic to the identity functor but that doesn't mean anything about 'a vector space being isomorphic to its dual'".
Why not? I've followed exactly the same recipe for both of them, using the notion of "natural transformation" as I was supposed to.
"Sure, but the result is interesting only in the case of $**$ because your definition of $*$ depended upon arbitrary choice ..."
Conclusion
All attempts to explain why I haven't really shown that a finite dimensional vector space is naturally isomorphic to its dual seem to invoke circular reasoning.
I can only conclude that if the notion of natural transformation is going to be used to formalise the concept of "independent of arbitrary choice" then something needs to be tightened up. My choice of $*_V$ was indeed arbitrary but it is not ruled out by the notion of natural transformation.
How could we proceed? Could the absence of choice be used to rule out the construction of $*_V$? Answers to an earlier question seem to suggest that is an irrelevant issue but in light of the above I'm not convinced. More generally, does this kind condition perhaps only make sense in a constructive or intuitionistic setting? I have a clue about how to formalise this condition in type theory via parametricity, so perhaps that is the key!
(This question is similar to an earlier one. I'm not convinced by the answer. It seems to be making an objection of the third form above, which seems circular to me.)