A novel polymerizable benzophenone photoinitiator containing acryloxy (BPA) was synthesized. The photopolymerization of photosensitive methacrylic-silicone resins (MASR) initiated by BPA was studied. Results show that BPA is an efficient photoinitiator, which could generate radicals from the photolysis reaction and be consumed via copolymerizing with MASR. The designed UV-curing silicone resins system initiated by BPA showed a high carbon-carbon double bonds conversion above 80% after 20 s UV radiation. In addition, reduced graphene oxide (rGO)-TiO2 composites were elaborated by hydrothermal reaction. The synergistic effects from graphene and TiO2 further enhanced the carbon-carbon double bonds conversion of MASR to 86% with 15 s UV irradiation, demonstrating that the incorporated rGO-TiO2 significantly improve the formulation UV-curing reactivity. Additionally, UV-cured MASR with rGO-TiO2 showed an excellent thermal stability. This work proposes an efficient strategy to improve the polymerization degree of UV-curable photosensitive silicone resins.