Methacrylate-terminated 4-arm star-shaped e-caprolactone oligomer (ME4CLO) was synthesized by reaction of hydroxy-terminated 4-arm star-shaped e-caprolactone oligomer (H4CLO) having a degree of polymerization per one oligocaprolactone chain, n = 5 and methacryloyl chloride in the presence of triethylamine. The ME4CLO was photo-cured with methacrylate-substituted polysilsesquioxane (ME-PSQ) or mercaptopropyl-substituted polysilsesquioxane (SH-PSQ) at the weight ratios of 16/0, 16/1, 16/2 and 16/4. Fourier transform infrared spectroscopy (FTIR) of the cured hybrid composites revealed addition polymerization of the methacryloyl groups and/or a thiol-ene reaction of methacryloyl and mercapto groups. Transmission electron microscope (TEM) observation revealed phase-separated spherical particles with a diameter of 5 μm for the cured ME4CLO/ME-PSQ 16/2, while the cured ME4CLO/SH-PSQ 16/2 had unstructured, finer-sized particles. DSC analysis revealed crystallization of the oligocaprolactone chain was largely disturbed by the crosslinking reaction and that the cured ME4CLO/ME-PSQ and ME4CLO/SH-PSQ 16/1 showed a higher glass transition temperature than cured ME4CLO. Tensile modulus of cured ME4CLO/ME-PSQ increased with increasing ME-PSQ content while cured ME4CLO/SH-PSQ showed a lower tensile modulus than cured ME4CLO.