The effect of Cu addition varied from 0 to 4 mass% on the corrosion resistance and electrochemical response in Ni–Co–Cr–Mo alloys was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy, and Mott–Schottky analysis. Results indicate that the Ni–Co–Cr–Mo alloy with 2 mass% Cu exhibited the most superior corrosion resistance, and the presence of Cu greatly influenced the outer porous layer. The Ni–Co–Cr–Mo alloys’ corrosion resistance was not simply increasing with copper addition increasing from 0 to 4 mass%. The X-ray photoelectron spectroscopy etching analysis was also conducted to illustrate the fraction of Cu at various depths in the passive film, and the results reveal that a maximum limit on Cu content (appropriately 3.10 mass%) existed in the outermost surface in the present condition. Among the studied alloys, the Ni–Co–Cr–Mo–2%Cu alloy formed the thickest passive film with the lowest donor density.