Polymer Dispersed Liquid Crystal (PDLC) films investigated in this work are obtained by phase separation induced by photopolymerization of a homogeneous ‘prepolymer/liquid crystal’ mixture. We show a close relation between the formulation/conditions of preparation of the materials, their morphology and their electro-optical properties. The effect of the mutual compatibility of the prepolymer and the liquid crystal on film performances is investigated using ‘model systems’ that consist of pure components. Finally, both SALS experiments and a Fourier Transform procedure lead to a simple model in which LC domains are separated by polymer walls.