Porous NiTi shape memory alloys were fabricated by thermal explosion method using different Ti and Ni powder as initial materials. The effect of process parameters including heating rate, and particle size of Ti on pore characteristic and phase composition was analyzed. Microstructure, phase composition, and mechanical properties were studied by SEM, XRD, and compression test, respectively. The mechanism of thermal explosion reaction was studied. The results show higher heating rate and smaller Ti particle size result in higher porosity and bigger pores. The thermal explosion reaction starts with the melting of a eutectic between β-Ti(Ni) and Ti2Ni and the main phases of as-reacted products are TiNi phase which are the desired phases. NiTi2 and TiNi3 phases are also present in small amounts. The content of TiNi phase increases with increasing heating rate or decreasing Ti particle size. The compressive strength and Young’s modulus of compacts decrease with the increase of the porosity.