In this work, aiming at a UV-curing 3D printing process with liquid crystal display (LCD) irradiation, a novel free-radical/cationic hybrid photosensitive resin was designed and prepared. After testing, the results showed that the acrylate monomers could be polymerized through a free-radical mechanism, while the epoxides were polymerized by a cationic curing mechanism. During the process of UV-curing, the acrylate and epoxide polymers were crosslinked and further locked together by non-covalent bonds. Therefore, an interpenetrating polymer network (IPN) structure could be formed through light-curing 3D-printing processes. Fourier transform infrared spectroscopy (FT-IR) revealed that the 3,4-epoxy cyclohexyl methyl-3,4-epoxy cyclohexyl formate and acrylic resin were both successfully involved in the UV-curing process. Furthermore, in order to make the 3D-printed objects cured completely, post-processing was of great importance. The results from the systematic study of the dynamic mechanical properties of the printed objects showed that the heating treatment process after UV irradiation was very necessary and favorable for the complete cationic polymerization of UV-6110 induced by Irgacure 261. The optimum heating treatment conditions were achieved at a temperature of 70 °C for 3 h.