In this paper, the rapid synthesis of nanostructured NiTi–Ni3Ti intermetallic alloy from titanium and nickel powders through mechanical alloying followed by microwave-assisted sintering process was investigated. The sintered samples at different temperatures exhibited major phases of NiTi– B2 and Ni3Ti, and minor phases of NiTi–B19′ and Ti2Ni. The density, porosity and microhardness of the sample varied based on the sintering temperature, in which the highest density and microhardness (~750 H V) were obtained at sintering temperature of 1100 °C. Based on the results of this research, the microwave-assisted sintering can be applied to fabricate Ni–Ti alloys with improved mechanical properties for biomedical applications.