To establish the relationships between composition, microstructure, and properties, the influence of Al addition on microstructure and properties of Cu–Fe-based coatings by laser induction hybrid rapid cladding was studied. With increasing Al content, the main diffraction peaks of ε-Cu phase are weakened but those of α-Fe phase are strengthened, the size of Fe-rich particles generally increases but the dendrite arm spacing is further reduced, and the number of Cu-rich grains precipitated inside the Fe-rich particles increases but the size reduces. Moreover, when the amount of Al is increased, the improvement in electrochemical resistance is attributed to large amounts of fine Cu-rich grains precipitated inside the Fe-rich particles, which results in large anode–small cathode effect. The microhardness also increases with Al content and the microhardness of Cu53.5Fe36Al10C0.5 coating is approximately 2.4 times higher than that of copper alloy substrate.