Calcium phosphate glasses in which part of CaO was replaced by TiO2 were prepared by the conventional melt quench method. The structures and their thermal properties were studied by XRD, Raman and DSC techniques. The results show that, TiO2 and calcium phosphate form homogeneous glass with the amount of the additive less than 3 mol%. The glasses matrix generates a Ca2P2O7 and CaTi4(PO4)6 crystal phase with the amount of the additives in the range of 6~12 mol%. With the addition of TiO2, the structural changes of the glass system are from metaphosphate to pyrophosphate and orthophosphate. With the TiO2 less than 3 mol%, the cohesion of the glasses structure and the glasses thermal stability is enhanced, and the glasses transition temperature is gradually increased.