In this research, in order to realize the phase-separated composite organic film (PSCOF) structure of liquid crystal (LC) cell, we have researched in detail its fabrication conditions. Nematic and ferroelectric LCs have been used for the investigation. Furthermore, we try to realize the PSCOF cell by using photocurable LC monomers as polymer materials. The contact angle has been measured in LC and polymer materials to lots of alignment films. As a result, it is found that the important factors for the fabrication of PSCOF structure are the wettability of LC materials to alignment film and the molecular weight of monomer.