Consider a first order language with a certain signature $\sigma$ (e.g. $(+,0)$). A tautology is a $\sigma$-formula (i.e. a first order formula with the standard logical symbols, variables, and $+,0$) that is true for all $\sigma$-structures.
So we have already a set $S$ of models (namely the set of all $\sigma$-structures) in which the following property is true:
Definition. Given a set of models $S$, the set $\Phi_S$ is defined as the set of formulas $\phi$ such that $\phi$ is true in every model in $S$.
Definition. $S$ satisfies property $P_S$ iff $\Phi_S$ exactly equals the set of tautologies.
But presumably we can remove some models from the set while still retaining the property $P_S$. My question is, is there a smallest set $S$ of models that satisfies $P_S$? i.e. a smallest set of models such that only the tautologies are true for all of them.
By counting sentences (per Hagen von Eitzen's comment), there is a countable $S$ with the property you want. Combined with the Lowenheim-Skolem theorem, there is in fact a countable $S$ consisting entirely of countable structures with the desired property.
Refining things further, we have results from computability theory. For every satisfiable sentence $\sigma$ there is an infinite computable binary tree $T_\sigma$ such that every path through $T_\sigma$ computes a model of $\sigma$. So every basis theorem for closed sets in Cantor space yields such an $S$. For example, the set of structures with domain $\subseteq\mathbb{N}$ which are low - of which there are only countably many - has the desired property.
It's worth pointing out that we can ask the same question about other logics. Hagen von Eitzen's comment applies in general - if $\mathcal{L}$ is a logic with $\kappa$-many sentences, we can find a desired $S$ with cardinality $\kappa$. We can further control $S$ by computing the Lowenheim number of $\mathcal{L}$, namely the least $\lambda$ such that every satisfiable $\mathcal{L}$-sentence has a model of size $<\lambda$. For example, the Lowenheim number of the nicest infinitary logic $\mathcal{L}_{\omega_1,\omega}$ is just $\aleph_0$ as with first-order logic, while the Lowenheim number of second-order logic is gigantic.
(A good proof that the Lowenheim number of $\mathcal{L}_{\omega_1,\omega}$ is $\aleph_0$ can be found in Marker's recent book. On the other hand, here's a delightfully stupid proof: if $\varphi$ is a satisfiable $\mathcal{L}_{\omega_1,\omega}$-sentence, take a forcing extension $V[G]\supset V$ in which some model of $\varphi$ is countable and apply Mostowski absoluteness to the sentence "$\varphi$ has a countable model.")