The failure of a chromium plating layer on the surface of a piston rod was analyzed, and an Ni-based alloy mixed with a niobium (Nb) composite coating was investigated by means of stereomicroscopy, metallographic microscopy, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Vickers hardness testing, and wear testing. The results show that penetrating cracks were present in the chromium layer. Subsequently, the corrosion intensified, resulting in the bubbling, cracking, and peeling of the chromium layer. The cladding layer presented a structure morphology of planar crystalline at the bottom, dendritic at the middle, and equiaxial crystalline at the top. The solidification parameters, which were derived from simulation results, confirmed that the ratios between temperature gradient (G) and solidification speed (S) decreased, and the values of the cooling speeds increased from the bottom to the top of the cladding layer. With an increase in Nb content, the structure became gradually refined and uniformly dense. The cladding layer of the Ni-based alloy mixed with Nb was mainly composed of γ-Ni, Cr23C6, Cr7C3, NbC, and Ni3Nb. NbC could be formed in situ and presented itself in four forms: particles, dendrites, polyhedrals, and networks. The microhardness of the coating with 15% added Nb was enhanced to 400 HV0.2, and the wear resistance thereof was 11.14 times higher than the substrate. After the 15% Nb coating had aged for 16 h, the diffraction peak intensities of Cr23C6 and Cr7C3 significantly increased, and the volume fraction of granular NbC increased from 1.67% to 2.54%. The microhardness was enhanced to 580 HV0.2, and the wear resistance thereof was better than that of the chromium plating layer.