Pixel-isolated liquid crystal (PILC) mode investigated in this work is obtained by phase separation induced by the anisotropic photoreaction of a prepolymer containing a vinyl cinnamate monomer. It was found that the incorporation of the cinnamate monomer was an efficient method for the control of the interfacial properties between LC and polymer walls. Polarization-selective photo-curing of the prepolymer containing a cinnamate monomer was closely related with the liquid crystal orientation at the polymer wall boundary resulting in electro-optical performance improvement.