Single-phase NiTi was fabricated through the thermal explosion mode of combustion synthesis of mechanically activated powders. Combustion and ignition temperatures of combustion synthesis were investigated in different milling times. In this process, equiatomic powder mixtures of nickel and titanium were activated by planetary ball mill and pressed into disk-shaped pellets then heated in a tube furnace, while temperature-time profile was recorded. X-ray diffraction analysis (XRD) was performed on milled powders as well as synthesized samples. Scanning electron microscopy (SEM) was also used to study the microstructural evolution during milling. The results showed that there was a threshold milling time to obtain single-phase NiTi. It was also seen that the ignition temperature and combustion temperature were reduced significantly by increasing milling time.