Ni/WC/graphene oxide (GO) composite cladding fusion coatings were fabricated through the vacuum cladding technique on a medium carbon structure steel (45# steel) substrate whose carbon content was 0.45 ± 0.03%. The microstructural characteristics, phase composition, and electrochemical polarization characteristics of the composite cladding fusion coatings were analyzed with scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and the electrochemical workstation CHI660E. Results show that the microstructure was compact and was micro-crack free, and without inclusions or other defects. It was comprised of four micro-zones, namely, the composite, transition, diffusion fusion, and diffusion-affected zones with thicknesses of approximately 4 mm, 1 mm, 20 μm, and 250 μm, respectively. The main phases of the composite coating were γ-Ni solid solution, WC, Cr 7 C 3 , Ni 2.9 Cr 0.7 Fe 0.36 , Cr 23 C 6 , Ni3Fe, Ni 3 Si, Ni 3 B, W 2 C, and C. The self-corrosion potential of the composite coatings had increased by 0.3269 V compared with that of the substrate, and the corrosion current density of the composite coatings had decreased by nearly two orders of magnitude. The Ni-based solid solution region with relatively high C and Cr contents was difficult to dissolve.