In this study, TEOS-VTES-CaCl2hybrids were synthesized via sol-gel method with different molar ratios (T0) VTES: TEOS1:0; (T1) VTES: TEOS1:1; (T2) VTES: TEOS1:2; (T3) VTES: TEOS 1:3 and, (T4) VTES: TEOS 1:4, respectively. Development of a calcium phosphate (CP) layer on their surfaces was studied by soaking them in a simulated body fluid (SBF). The consequent formation of the CP layer and structural discrepancies of the formed layer of various samples were studied by means of appropriate techniques such as X-ray diffractometry, Fourier transform infrared spectroscopy and scanning electron microscopy equipped with an energy dispersive system (EDS).It was found that the rate of in-vitro apatite formation on hybrid surface decreased with increasing the amount of TEOS precursor. For biomaterials application the best surface in terms of in-vitro bioactivity, adsorbed protein amounts and thermal stability is the T2 surface containing VTES: TEOS1:2.