Organic-inorganic composites have received increasing attention because such composites exhibit improved optical, electrical, thermal, and mechanical behaviors by combining properties of both organic polymers and inorganic compounds. However, tensile strength is enhanced generally at the cost of decreasing ductility, which is not suitable for biomedical applications where tissue-like elasticity is required. In this study, multilayered poly(vinyl alcohol) (PVA)/silica composites were synthesized, which achieved a significant enhancement in tensile strength and ductility. The chemical structure, thermal stability, and fracture morphologies of multilayered films were investigated to analyze the reinforcement mechanism. The results showed that extensive plastic tearing took place in monolayered composites with low-silica contents and in all multilayered ones, whereas the monolayered composites with high-silica contents were dominated by brittle fracture. For layered composite with 30 wt% silica in the second layer, the elongation at break is 237.8%, which is 3.21 times that of monolayered 30% SiO2/PVA 74.0%. Also its tensile strength is 37.8 MPa, which is 1.52 times that of monolayered 30% SiO2/PVA 24.8 MPa. These improved mechanical properties broaden its potential application, especially the applications of PVA in medical materials, which are intensely discussed as biomaterials. POLYM. ENG. SCI., 50:689-696, 2010. (C) 2009 Society of Plastics Engineers