The glass-ceramics in the system SiO2-CaO-Na2O-P2O5, well known as an excellent biomaterial for bone tissue engineering was synthesized by aqueous sol-gel method. The thermal decomposition behaviour of the gel was studied using thermo-gravimetric analysis and differential scanning calorimetry. The crystallisation behaviour of glass was characterised by XRD phase analysis, Fourier Transform IR Spectroscopy, and SEM. The results revealed that the crystallization occurred at a temperature of 700 deg C and the glass-ceramics was composed of primary phases; combetite (Na2Ca2Si3O9) and devitrite (Na2Ca3Si6O16). Microstructural analysis revealed that there were simultaneous sintering and crystallization processes occurring during heat treatment. Sintering kinetics of the glass-ceramics powder was also investigated.