Spherical bridged polysilsesquioxane nanoparticles with thiol groups (BPS-SH) were prepared by the reduction of BPS with disulfide groups after the base-catalyzed hydrolysis and condensation reaction of bis(triethoxysilylpropyl)disulfide. The average size of BPS was around 100 approximate to 300nm. Hydroxyethyl methacrylate (HEMA)-initiated polycaprolactone (PCL) was synthesized by ring-opening polymerization of caprolactone under the co-initiation of HEMA and Sn(Oct)(2). New nanocomposites of BPS-SH and HEMA-PCL were fabricated by the photo-induced chemical reaction under a photoradical generator and ultraviolet light. BPS was fully and continuously covered with PCL, which resulted in the rough surface of BPS nanoparticles as well as the connected BPS nanoparticles together.