A novel water-soluble hyperbranched photosensitive polysiloxane urethane acrylate (WHBPSUA) was synthesized, and its structure was characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, and H-1 NMR It was found that WHBPSUA possesses good compatibility with a number of acrylate monomers and deionized water. The effect of monomers on the photopolymerization kinetics of WHBPSUA was investigated by real-time infrared spectroscopy (RT-IR). The results showed that the resin that is consisted of WHBPSUA with common acrylic monomers exhibits high polymerization rate and double bond conversion. Additionally, it could form a regular image under UV irradiation through a patterned mask. More importantly, the microstructure on the surface of UV-cured WHBPSUA films was characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. It is proved that the increase of the degree of cross-linking and Si content of the UV-cured WHBPSUA films leads to excellent flexibility, toughness, and heat resistance of UV-cured WHBPSUA films.