Bioactive ORMOSILS (organically modified silicate), PDMS-CaO-SiO2-P2O5 with five different P2O5 content (0, 0.01, 0.03, 0.06, 0.09 mol%) have successfully been synthesized by sol-gel process. The hybrids have been prepared with polydimethylsiloxane (PDMS), tetraethoxysilane (TEOS), calcium nitrate tetrahydrate [Ca(NO3)2 4H2O] and triethyl phosphate (TEP) as starting materials and subsequently soaked into the simulated body fluid (SBF) for different period of time and the bioactivity of hybrids was determined by examining the apatite formation on the surface of the specimen by FT-IR, Thin-Film X-ray Diffraction, and Scanning Electron Microscopy (SEM). All of the prepared samples with different P2O5 content showed in vitro bioactivity. It was observed that the increase in P2O5 content up to 0.03 mole % increases the apatite formation compared to P2O5- free hybrids. However, further increase in P2O5 concentration slows down the formation of the apatite layer most probably due to the decrease of pH of SBF by dissolution of a large amount of phosphate ions.