yeah but silicone will pick up microscopic details, so you will retain the grooves from your print doing it that way, which retain moisture, which gives bacteria a chance to grow.
Might also be fun to experiment with the opposite side: 3D print the mold and use it directly, then dip that in silicone to coat it and eliminate the artifacts that way. Plus then you could have the outer layer be a softer composition, like an overmolding, which might give an interesting feel.
It just won't show up with like a linen texture or something.
Body safe silicone is very thick, you'll have a very hard time getting an even coating.