A novel approach to fabricate epoxy-based polymer-stabilized liquid crystals (EPSLCs) via the cationic photopolymerization of liquid crystalline epoxide in mesogenic solvents was presented. The photoinitiated cationic polymerization of liquid crystalline epoxide in different mesogenic solvents was compared and the liquid crystalline epoxy polymer (LCEP) network can only be formed in the particular solvents. The different photo-curing behaviors of the liquid crystalline epoxide in various solvents may be ascribed to the solvent effect and the content of the nucleophilic groups had a decisive influence on the formation of the LCEP network. The epoxy polymer/liquid crystal (LC) composites were also prepared by the cationic photopolymerization of different epoxy monomers in LC solvent. The morphology of the epoxy polymers in the composites and the change of the arrangement of LC molecules before and after polymerization were also studied. Moreover, the stabilizing effect of the LCEP network on the LC molecules was also characterized by the electric-optical performance test. This report can offer an innovative technique to fabricate EPSLCs and provide a promising means for the development of functional epoxy polymer composites.