The mechanically activated self-propagating high-temperature synthesis (MASHS) technique and the mechanically activated annealing process (M2AP) were used to produce NiAl intermetallic compound. Rietveld analysis of X-ray diffraction data was used to characterize the mechanically activated powders, MASHS and M2AP end-products. Two-phase (B2+L12) nickel aluminide intermetallic compounds were synthesized by the mechanically activated volume combustion synthesis (MASHS). A single phase B2 NiAl was formed when mechanically activated annealing process (M2AP) was performed. Starting from a mixture of elemental pure powders, both M2AP and MASHS milling processes lead to nanostructured powders. Structural analysis deduced from the Rietveld refinement of X-ray diffraction patterns of NiAl compounds synthesized by SHS after a milling of 6 h show the formation of β-NiAl phase with a cell parameter a = (0.2885 ± 1.2618 × 10−4) nm. The average crystallite size is D = (44.6421 ± 2.4263) nm and the microstrains values are close to those of metallic alloys τ = (0.2142 ± 1.6186 × 10−2)%. Finally, scanning electron microscopy (SEM) was carried out to characterize the microstructure of end-products.