A photosensitive silicone-containing polyurethane acrylate prepolymer (Si-IPDI-HEA) was synthesized and characterized adequately by FTIR, H-1 NMR, and GPC analyses. The effect of the monomers on the photopolymerization kinetics of Si-IPDI-HEA was investigated by real-time infrared spectroscopy (RT-IR). The results showed that the resin of Si-IPDI-HEA with common acrylic monomers exhibited a high polymerization rate and double-bond conversion. The influence of the monomer and silicone on the microstructure and properties of the UV-cured film also was systematically studied. It was found that, with the increase of the functionality of the monomer, the thermostability, T-g, hardness, tensile strength, tensile modulus, and dispersion surface energy of the UV-cured film were increased, whereas the contact angle and elongation at break were decreased. The introduction of silicone into the prepolymer could enhance the thermostability of the UV-cured film, and reduce the dispersion surface energy by the change of the microstructure. More importantly, the leather finishing agent containing Si-IPDI-HEA has excellent comprehensive performance and potential application in the leather finishing agent.