Ni–Al powder and Ni–Al composite coatings were fabricated by twin-wire arc spraying (TWAS). The microstructures of Ni-5wt%Al powder and Ni-20wt%Al powder were characterized by scanning electronic microscopy (SEM) and energy dispersive spectroscopy (EDS). The results showed that the obtained particle size ranged from 5 to 50 μm. The morphology of the Ni–Al powder showed that molten particles were composed of Ni solid solution, NiAl, Ni3Al, Al2O3, and NiO. The Ni–Al phase and a small amount of Al2O3 particles changed the composition of the coating. The microstructures of the twin-wire-arc-sprayed Ni–Al composite coatings were characterized by SEM, EDS, X-ray diffraction (XRD), and transmission electron microscopy (TEM). The results showed that the main phase of the Ni-5wt%Al coating consisted of Ni solid solution and NiAl in addition to a small amount of Al2O3. The main phase of the Ni-20wt%Al coating mainly consisted of Ni solid solution, NiAl, and Ni3Al in addition to a small amount of Al and Al2O3, and NiAl and Ni3Al intermetallic compounds effectively further improved the final wear property of the coatings. TEM analysis indicated that fine spherical NiAl3 precipitates and a Ni–Al–O amorphous phase formed in the matrix of the Ni solid solution in the original state.