An experimental investigation is performed into the microstructure and mechanical properties of Mo-doped (0, 3, 6, 9,12 and 15 wt% Mo) NiAl coatings deposited on medium carbon steel substrates with a laser cladding process. It is shown that as the Mo content increases, the density of the Mo-rich phase network structure increases and the grain size of the laser-clad coating reduces. Moreover, the hardness and wear test results indicate that a higher Mo addition not only increases the strength of the NiAl coating, but also improves its toughness and wear resistance. With a combination of alloy design and the role of laser cladding process, this study provides a potential guideline for practical application of intermetallic compound in the future. In general, with a combination of alloy design and the role of laser cladding process in this study provide a useful source of reference for extending the applications of NiAl composite coatings in the aerospace field and other advanced industries.