The crystallization behaviour of the laser synthesized nanometric amorphous Si3N4 powders with the particle size of 15 nm in diameter has been studied between 1200° and 1700℃ by XRD,TEM and FTIR techniques. A small amount of β-Si3N4 formed at 1250℃ and increased slowly until the α- β transformation happened at 1700℃, whereas α-Si3N4 appeared at 1300℃ andincreased rapidly between 1500-1600℃. The formation of β phase at the lower temperature was caused by the nitridation of free Si due to the preexisted β-nuclei in the Si3N4 particles, whereasthe α phase was formed by solid crystallization from the amorphous matrix. There were α and β SiC formed at 1700℃ due to the presence of Sio and Co gases in the system. FTIR analysis shows that two new IR absorption at 1356 and 1420 cm-1, and an overall strong absorption in wide wavenumber range resulted from the powders annealed at 1600 and 1700℃ respectively The crystallization behavior of the laser synthesized nanometric amorphous Si3N4 powders with the particle size of 15 nm in diameter has been studied between 1200 ° and 1700 ° C by XRD, TEM and FTIR techniques. A small amount of β-Si3N4 formed at 1250 ° C and increased The formation of β phase at the lower temperature was caused by nitridation of free Si due to the preexisted β There were α and β SiC formed at 1700 ° C due to the presence of Sio and Co gases in the system. FTIR analysis shows that two new IR absorption at 1356 and 1420 cm-1, and an overall strong absorption in wide wavenumber range resulted from the powders annealed at 1600 and 1700 ° C respectively