In this study, a Fe-Ni-Cr composite coating was applied to the surface of gray cast iron using the laser cladding method. Its phase and microstructure were investigated, as well as sliding friction and wear tests were performed at room-temperature and high-temperature. The specific conclusions were as follows: the main phases of the coating are γ-(Fe, Ni), Fe₅C_2,F₃C, and Cr₇C₃. F₃C had an excellent bonding property and was the main component of the transition zone between the coating and the substrate, resulting in a good metallurgical bonding between the coating and the substrate. Due to the undercooling degree, the microstructure of the coating from the heat-affected zone to the top of the coating gradually changed from columnar crystals to cellular crystals, dendrites, and equiaxed crystals, which had the effect of fine-grain strengthening and improving the coating’s hardness and wear resistance. At room temperature, the substrate’s wear mechanism was primarily abrasive wear, while at high temperatures, it was oxidation and adhesion wear. The wear mechanisms of the coating and substrate materials at room temperature were mainly abrasive wear. The thermal oxidation reaction became more severe as the test temperature rose, and the composite oxide film formed on the coating’s surface and alleviated adhesive wear and abrasive wear, which was one of the reasons for the coating’s ability to reduce friction coefficient and wear loss.