The relationship between chemical structures of monomers, especially their alkyl chain length, with morphology and electro-optical properties of the corresponding polymer/liquid crystal (LC) films were investigated. A dependence of electro-optical properties on the type of monomer used to prepare the films is demonstrated and explained. We report on the memory effect of polymer/LC films, which are prepared using four biocompatible acrylic and methacrylic monomers. These results were correlated with observations of the sample morphologies by polarizing optical microscopy. Samples based on acrylic and methacrylic monomers and 5CB were studied after polymerization, with and without application of an electric field.