As a follow-up to this question, let $\mathcal C$ be a category and $\mathcal S \subseteq \mathcal C$ a class of objects. Say that $\mathcal S$ is weakly generating if the functors $Hom_{\mathcal C}(S,-)$ are jointly conservative, for $S \in \mathcal S$. That is, a map $X \to Y$ in $\mathcal C$ is an isomorphism if and only if it induces a bijection $Hom_{\mathcal C}(S,X) \to Hom_{\mathcal C}(S,Y)$ for each $S \in \mathcal S$.
Question 1: Does the homotopy category of spaces admit a small generating set? (For example, as Simon Henry asks, do finite CW complexes work? How about the spheres?)
Of course, by Whitehead's theorem, the homotopy category of pointed connected spaces admits a generating set given by the spheres. But I'm not sure about unpointed spaces.
Note that the singleton set comprising the contractible space $\ast$ is a generator in the $\infty$-category of spaces, since $X \to Y$ is an equivalence if and only if $Map(\ast, X) \to Map(\ast,Y)$ is an equivalence. But passage to the the homotopy category discards the higher homotopy of the mapping spaces.
Question 2: More generally, if $\mathcal C$ is an accessible $\infty$-category, then does the homotopy category $h\mathcal C$ admit a small generating set? What if we assume that $\mathcal C$ is presentable?
Again, if $\mathcal C$ is $\kappa$-accessible, then the class $\mathcal C_\kappa$ of $\kappa$-compact objects forms a generating set in $\mathcal C$, but it's not clear if it forms a generating set in $h\mathcal C$. In fact, I think that Question 2 (in the "presentable" case) is equivalent to Question 1: if the answer to Question 1 is affirmative, so that $\mathcal S$ is a generating set for the homotopy category of spaces and $\mathcal T$ is a generating set for $\mathcal C$, then the set of spaces $S \ast T$ for $S \in \mathcal S, T \in \mathcal T$ forms a generating set for $h\mathcal C$. Here $\ast$ denotes copowering.
One result in this direction is Rosicky's Theorem, which says (in model-independent language) that if $\mathcal C$ is a presentable $\infty$-category, then the canonical functor $h\mathcal C \to Ind_\kappa(h\mathcal C_\kappa)$ is essentially surjective and full for some $\kappa$. For my purposes, it would suffice to know that this functor is conservative for some $\kappa$.