Schwartz space $\mathcal S(\mathbb R^n, \mathbb C)$ is a dense subspace of $L^2(\mathbb R^n,\mathbb C)$ that appears frequently in physics, because the position operators $X_i$ and momentum operators $P_i$, defined by $(X_if)(x) = x_if(x)$ and $P_if=-i (\partial/\partial x_i)f$ are defined and well behaved on it.
However, there are many other spaces of test functions that could be used (and sometimes are used) in this context, and elsewhere in functional analysis. Still the Schwartz functions seem to appear the most often, so I wonder if they are "natural" or "canonical" in any sense. Are there any natural characterizations of $\pmb{\mathcal S(\mathbb R^n, \mathbb C)}$? For example, something like "Schwartz space is the unique subspace of $L^2$ such that ..." or "Schwarz space is the largest subspace of $L^2$ such that ...".
I think I once saw a such a characterization in terms of the position and momentum operators above, along the lines of "the largest subspace such that $X_i$ and $P_i$ are simultaneously defined," or something like that. But I cannot find it now, and I may be misremembering completely.
Yes, there are two such properties (in fact, they might be equivalent, but I'm not 100% sure of that)
Fourier Transforms are defined over the space of all integrable functions. However, it is not (in the function-sens) bijective; meaning some functions do not have an inverse Fourier transform. However, like for any operation you can restrict the Fourier Transform to a subspace over which it is a bijection, and the biggest such space is $\mathcal{S}$.
In deed, you can show that when studying integrable functions the dual of the dual is isomorphic to the original space. This is what allows to construct distribution theory (dual of test function space). Some subspaces of integrable functions (like $L_1$ or test functions, or $L_2$) have duals that are either "bigger" or "smaller" than themselves. Schwartz is the biggest space whose dual is basically itself.
Finally (to get back to physics) a great property of Schwarz space is also that you can use Stokes formula to the infinite limit: $$\int_\Omega \partial f = \int_{\partial \Omega} f = 0$$ And like you mentioned, it is dense in $L_2$. This allows (you can make it rigorous by a lot of painful proofs, or just assume it "physics' style") to extend many properties of Schwartz (especially the previous one) to $L_2$ (the actual physical space) by considering a sequence of functions of $\mathcal{S}$ converging towards something in $L_2$.
So sometimes, in physics, we assume being in Schwarz wile in fact not being in it, simply because, in the limit, it doesn't really matter, so we might as well for shortening the proofs.