The Ni3Al and Ni3Al-B-Cr alloys were fabricated by the self-propagation high-temperature synthesis with hot extrusion method. Their microstructure and mechanical properties were studied by using combination of X-ray diffraction, optical microscopy, transmission electron microscopy and compression test. Analysis of X-ray spectra exhibited that the elemental powders had been transformed to the Ni3Al phase after the self-propagation high-temperature synthesis processing. Microstructure examination showed that the alloy without extrusion consisted of coarse and fine grains, but the subsequent hot extrusion procedure homogenized the grain size and densified the alloy obviously. Transmission electron microscopy observations on the Ni3Al alloy revealed that Ni3Al, γ-Ni and Al2O3 particles were the main phases. When the boron and chromium were added, besides the β-NiAl phase, α-Cr phase and some Cr7Ni3 particles with stacking faults inside were observed. In addition, a lot of substructure and high-density dislocation arrays were observed in the extruded part, which indicated that the subsequent extrusion had led to great deformation and partly recrystallizing in the alloy. Moreover, the subsequent extrusion procedure redistributed the Al2O3 particles and eliminated the γ-Ni. These changes were helpful to refine the microstructure and weaken the misorientation. The mechanical test showed that the self-propagation high-temperature synthesis with hot extrusion improved the mechanical properties of the Ni3Al alloy significantly. The addition of B and Cr in Ni3Al alloy increased the mechanical properties further, but the compressive strength of the alloy was still lower than that synthesized by combustion. Finally, the self-propagation high-temperature synthesis with hot extrusion was a good method to prepare Ni3Al alloy from powder.