The equation is a condition that an electric field $\mathbf{E}$ must meet to be a "valid" field for the situation in question, which is specified (at least in part, though this is tagged "electrostatics") by the charge distribution, $\rho$.
The fact that a differential equation must be satisfied logically implies that the any functions going into it that might be solutions must be differentiable - if it's not, you cannot talk about the derivative to begin with to test if it satisfies the equation.
The same goes with Newton's laws of motion - you don't need to state that the position function be twice differentiable with respect to the time, that comes with the fact that that is necessary for it to even be a candidate to go into the equation in the first place.
Even more elementarily, it goes with algebraic equations:
$$\frac{1}{x} = 5$$
$x = 0$ doesn't solve the equation because the LHS is undefined. Likewise, if $\mathbf{E}$ is something non-differentiable, it does not satisfy
$$\nabla \cdot \mathbf{E} = \frac{\rho}{\epsilon_0}$$
because the left-hand side is undefined. Undefined can't equal a defined quantity.
There is no need to state as a postulate what is a logical consequence. You can, but it's redundant and generally speaking, independent axioms/postulates are preferred for the basis of theories.