Novel poly(ε-caprolactone)-organosiloxane hybrid containing amine group was synthesized through sol-gel method. Triethoxysilane end-capped poly(ε-caprolactone) was prepared by reaction with α,ω-hydroxyl poly(ε-caprolactone) and 3-isocyanatopropyl triethoxysilane. It was then hydrolyzed and co-condensed with aminopropyl triethoxysilane through sol-gel method. The success of hybridization was evaluated by FT-IR by new formation of siloxane group. Osteoblast-like cell responses were assessed on this new hybrid material for the potential application as a bone tissue engineering scaffold. The cell responses were compatible with those on pure poly(ε-caprolactone) used as a control.