An UV-curable polysiloxane-modified polyether polyurethane acrylate prepolymer (Si5E5PUA) was synthesized with polysiloxane (Q4-3667), polypropylene glycol (PPG-2000), isophorone diisocyanate (IPDI), diethanolamine and hydroxy ethyl acrylate (HEA) as raw materials. The structure of Si5E5PUA was characterized by Fourier infrared spectrometer (FT-IR), nuclear magnetic resonance (1H NMR and 29Si NMR) and gel permeation chromatograph (GPC). The viscosity, photopolymerization behavior and volume shrinkage in polymerization processes of Si5E5PUA systems with different monomers and glass transition temperatures of cured films were investigated. The results showed that the Si5E5PUA exhibited good compatibility with acrylate monomers. The systems of Si5E5PUA with different monomers had excellent photopolymerization efficiency and final double bond conversion was over 90%. The increase of functionality of the monomers could enhance the glass transition temperatures of cured films. The volume shrinkage of Si5E5PUA systems ranged from 3.3% to 5.6%.