For each $n>1$ we shall construct a first-order theory $T_n$ with exactly n countable models. Let $n>1$, consider the language $L_n=\left\{{R,c_1,...,c_n}\right\}$, where $R$ is a binary relation symbol, and each $c_n$ is a distinct constant symbol. Put $$\phi=\forall{x}\forall{y}(x\neq{c_1}\wedge{y\neq{c_2,...c_n}}\longrightarrow{¬Rxy})$$ and $$\psi=\forall{x}\forall{y}\forall{z}(x\neq{y}\wedge{x\neq{z}\wedge{y\neq{z}\wedge{Rxy}}}\longrightarrow{¬Rxz}).$$ Set $$T_n=\left\{{c_i\neq{c_j}:i\neq{j}}\right\}\cup\left\{{\phi,\psi}\right\}.$$ It is clear that $T_n$ is consistent, and thus by Lowenheim-Skolem theorem $T_n$ has a countable model. Let $\mathcal{M}$ be a countable model of $T_n$, then since $\mathcal{M}\models{\phi}$ we must have that either $R^{\mathcal{M}}=\emptyset$ or $R^{\mathcal{M}}=\left\{{(c_1,c_{n_1}),...,(c_1,c_{n_m})}\right\}$, but since $\mathcal{M}\models{\psi}$ we get that if $R^{\mathcal{M}}\neq{\emptyset}$, then $\left |{R^{\mathcal{M}}}\right |=1$.
Therefore we must have that either $R^{\mathcal{M}}=\emptyset$ or $R^{\mathcal{M}}=\left\{{(c_1,c_m)}\right\}$ for some $m\leq{n}$. It is clear that if $\mathcal{M}$ and $\mathcal{N}$ are models of $T_n$ with $R^{\mathcal{M}}=\emptyset$ and $R^{\mathcal{N}}=\emptyset$, then $\mathcal{M}\simeq{\mathcal{N}}$.
And also if $R^{\mathcal{M}}=\left\{{(c_1,c_i)}\right\}$ and $R^{\mathcal{N}}=\left\{{(c_1,c_j)}\right\}$, then $\mathcal{M}\simeq{\mathcal{N}}$ if and only if $i=j$, for $\mathcal{M}\models{c_i\neq{c_j}}$ for $i,j\in{\left\{{2,...,n}\right\}}$ with $i\neq{j}$
By Lowenheim-Skolem theorem each case has a countable model.
Thus $T_n$ has exactly $n$ countable models.
I would like to see others examples.
Thanks