This study aims to develop glass ceramics in the calcium phosphate system that exhibit suitable properties to be used for biomedical applications. Calcium phosphate glasses with the incorporation of small additions of MgO and TiO2 oxides were prepared in the pyro-and orthophosphate regions. The glass ceramics were prepared by a controlled powder sintering process through heat-treatment at different temperatures, as defined by results from differential thermal analysis (DTA). The composition of the crystalline phases precipitated in the glassy matrix as a result of heat treatments at different temperatures, ranging from 681 to 725 &DEG; C, was determined from X-ray diffraction data. The sequence of phase crystallization in the mother glass was also studied in situ using high temperature X-ray diffraction (HT-XRD) analysis. Results showed that the first phases that precipitated in the glass matrix were α-and β-Ca2P2O7 at 620 &DEG; C. A small amount of CaTi4(PO4)(6) appeared at 630 &DEG; C. At 650 &DEG; C the three phases α-Ca2P2O7, β-Ca2P2O7 and CaTi4(PO4)(6) were clearly presented with a small amount of TiP2O7 and finally at 660 &DEG; C all four phases were observed. Glass ceramics were also characterized using Raman and X-ray photoelectron spectroscopy. This study demonstrates that, by altering the heat treatment cycle, it is possible to prepare glass ceramics in the calcium phosphate system that contains different bioactive and biocompatible phases. © 2005 Published by Elsevier B.V.