That statement is something of a mathematical quagmire because there are lots of algebraic structures floating around, and the maps between them aren't explicitly "typed" (i.e., it's not exactly explicit what kinds of structures the homomorphisms are between)!
The notation $\operatorname{Hom}_{\Bbb C}(\Bbb C^2, \Bbb C^3)$ is just the set of all $\Bbb C$-linear maps from $\Bbb C^2$ to $\Bbb C^3$ (the subscript $\Bbb C$ is what tells us the maps are $\Bbb C$-linear). Recall that a $\Bbb C$-linear map $T: \Bbb C^2 \to \Bbb C^3$ is just a map that
"respects addition," so that $T(x + y) = T(x) + T(y)$ for vectors $x, y \in \Bbb C^2$, and
"respects (complex) scalar multiplication" so that $T(cx) = cT(x)$ for scalars $c \in \Bbb C$ and vectors $x \in \Bbb C^2$.
Another term for a linear map is a vector space homomorphism, hence the notation $\operatorname{Hom}_\Bbb C (\Bbb C^2, \Bbb C^3)$. Essentially, as other answers have pointed out, homomorphisms are just maps between algebraic structures (in this case, vector spaces) that "respect" the relevant operations (in this case, vector spaces are spaces in which we can add vectors together and multiply them by scalars, and each operation needs to be "respected").
Now, the sets $\operatorname{Hom}_\Bbb C (\Bbb C^2, \Bbb C^3)$ and $\operatorname{Mat}_\Bbb C(3, 2)$ can themselves be thought of algebraic structures (they are groups under composition/multiplication) but I would not worry about that! At least for now.
I would simply view the '$\simeq$' in $\operatorname{Hom}_\Bbb C (\Bbb C^2, \Bbb C^3) \simeq \operatorname{Mat}_\Bbb C(3, 2)$ as the claim that these two sets are in bijection: If you have a linear map $T\colon \Bbb C^2 \to \Bbb C^2$, there's an easy way to write down a $3 \times 2$ matrix $M_T \in \operatorname{Mat}_\Bbb C(3, 2)$: Just make the $i$th column of $M_T$ the image $T(e_i)$ of the standard basis vector $e_i \in \Bbb C^2$.
Now, if we want to consider the '$\simeq$' in $\operatorname{Hom}_\Bbb C (\Bbb C^2, \Bbb C^3) \simeq \operatorname{Mat}_\Bbb C(3, 2)$ as some kind of isomorphism of algebraic structures (not just between sets, i.e., a bijection), we would then need to worry about whether the relevant operations are preserved. If we're composing maps $S, T \in \operatorname{Hom}_\Bbb C (\Bbb C^2, \Bbb C^3)$, we'd need to verify that the corresponding matrices $M_S, M_T \in \operatorname{Mat}_\Bbb C(3, 2)$ multiply the way we'd expect. That is,
$$M_T M_S = M_{T \circ S}.$$
If you show this, then you'll have shown that the groups $\operatorname{Hom}_\Bbb C (\Bbb C^2, \Bbb C^3)$ and $\operatorname{Mat}_\Bbb C(3, 2)$ are isomorphic (provided you've already shown they're in bijection). The homomorphism could be made concrete as a map $M \colon \operatorname{Hom}_\Bbb C (\Bbb C^2, \Bbb C^3) \to \operatorname{Mat}_\Bbb C(3, 2)$ that sends a $\Bbb C$-linear map $T \in \operatorname{Hom}_\Bbb C (\Bbb C^2, \Bbb C^3)$ to the matrix $M_T \in \operatorname{Mat}_\Bbb C(3, 2)$ described above.
But unless your linear algebra class is way fancier than mine (and it very well may be), I would assume, not having done much group theory, that the statement is just pointing out that the two sets are in bijection, possibly "to be expanded upon later" or "plus other good stuff."