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Ni‐based alloy coatings are sprayed on 304 stainless steel substrates using a high velocity oxygen fuel spraying (HVOF) method. The corrosion‐wear behavior was analyzed using a “block on ring” corrosion‐wear system. This study mainly discusses the effect of different applied potentials on corrosion and wear interaction using scanning electron microscopy, transmission electron microscopy and X‐ray photoelectron spectroscopy (XPS). The results show that as the applied potential increases, the weight loss and corrosion current density of the nickel‐based alloy coating increase accordingly. Increasing the applied potential, the total loss of corrosion‐wear (Wtotal) of the coating increased significantly. Under high applied potential, the main factor for the serious damage is the interaction of corrosion and wear. In addition, the friction coefficient of the coating first increases and then decreases with increasing applied potential. The surface morphology of the passivation layer and the thickness of corrosion oxide can have an important influence on the corrosion‐wear process. Based on the XPS analysis results, the composition of the passive film formed on the surface of the coating in the process of corrosion‐wear includes NiO, Cr2O3, MoO2, and MoO42−.