Synthetic model of a ceramic-polymer composite, in which thin layer of bioactive silicate ceramic is molecular-hybridized onto surface of polydimethylsiloxane (PDMS) bulk, has been examined in the tetraethoxysilane (TEOS)-PDMS sol-gel system. A TEOS precursor solution of silica was subjected to hydrolysis and condensation on TEOS-PDMS precursor solution forming silica PDMS hybrid bulk through co-polymerization, producing single large transparent crack-free monolithic hybrid bulk. Spectroscopic characterizations complemented with microscope observation showed that the surface of this hybrid was bioactive silicate, and that the surface silicate was successfully hybridized with the bulk silica-PDMS hybrid without revealing a distinct interface. These suggest a synthetic process of bioactive composites which have bioactive functionally graded ceramic surfaces on polymers, and thereby function with various polymeric physical properties as well as with ceramic bioactivity. (c) 2005 Elsevier B.V. All rights reserved.