Effect of poly(ε-caprolactone) structure on the mechanical properties and apatite-forming ability of poly(ε-caprolactone)/silica composite was investigated. Star-shaped poly(ε-caprolactone) was used in the experiment and it was end-capped with 3-isocyanopropyl triethoxysilane following the reaction with tetraethyl orthosilicate by sol-gel method. It was heat-treated at 150 oC for 24 hours and then tensile mechanical and dynamic viscoelastic testings were conducted, respectively. Its bioactivity was evaluated by the apatite forming ability in simulated body fluid at 36.5 oC. Its tensile strength was about 22 MPa while elastic modulus was about 2.6 GPa when the content of poly(ε-caprolactone) was 60 wt.%. The formation of apatite crystals on its surface was confirmed after 1 week of soaking in the SBF. The high elastic modulus of this composite was explained in terms of its 3-dimensional network structure.