In order to study the effect of nano-CeO2 particles doping on the electrochemical corrosion behavior of pure Ni-Fe-Co-P alloy coating, Ni-Fe-Co-P-CeO2 composite coating is prepared on the surface of 45 steel by scanning electrodeposition. The morphology, composition, and phase structure of the composite coating are analyzed by means of scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The corrosion behavior of the coatings with different concentrations of nano-CeO2 particles in 50 g/L NaCl solution is studied by Tafel polarization curve and electrochemical impedance spectroscopy. The corrosion mechanism is discussed. The experimental results show that the obtained Ni-Fe-Co-P-CeO2 composite coating is amorphous, and the addition of nano-CeO2 particles increases the mass fraction of P. With the increase of the concentration of nano-CeO2 particles in the plating solution, the surface flatness of the coating increases. The surface of Ni-Fe-Co-P-1 g/L CeO2 composite coating is uniform and dense, and its self-corrosion potential is the most positive; the corrosion current and corrosion rate are the smallest, and the charge transfer resistance is the largest, showing the best corrosion resistance.