The effectiveness of electrospinning as a simple approach to disperse POSS into a polymer matrix at a nm-level has been assessed. Electrospun and cast films were prepared by dissolving CA and epoxycyclohexylisobutyl POSS in the solvent mixture acetone/DMAc. The membranes were characterized by SEM, TEM and WAXD. Whereas films produced by casting showed mu m-sized POSS crystals, thus suggesting a small affinity between the polymer matrix and the POSS molecules, those prepared by electrospinning were characterized by a nanometric POSS distribution. This is explained by considering the peculiar solvent evaporation mechanism, occurring during the electrospinning process, which allows to produce nanofibers characterized by a silsesquioxane dispersion similar to that present in solution.