Ni-based alloy powder (NiCrBSi) was applied to prepare coatings on Ti6Al4V by laser cladding to improve the wear resistance of the latter under corrosion. The scanning speed was found to be an essential parameter that could adjust the microstructure of the coatings. Changes in the microstructures of the coatings with the scanning speed were highlighted, and the relationships between the microstructures and microhardness, fracture toughness, corrosion, and corrosion wear resistance of the coatings were established. Results indicated that the matrix changes from Ti2Ni + TiNi to primary γ(Ni) + eutectics (γ(Ni) + Ni3Ti) with increasing scanning speed. Moreover, reinforcement phases changed from TiB2 + TiC (5 mm∙s−1) to TiB2 + TiC + Cr7C3 (11 mm∙s−1) to TiB2 + TiC + Cr7C3 + CrB (17 mm∙s−1). The average microhardness of the coatings first increased and then decreased, and the corresponding fracture toughness showed the opposite trend. The optimum combination of these properties was observed in the coating prepared at 11 mm∙s−1. This coating demonstrated excellent wear resistance in 3.5 wt.% NaCl solution, as well as a high corrosion potential, a low corrosion current density, and a low current density when the electrode initially entered a comparatively stable corrosion state. Moreover, compared with coatings prepared at other scanning speeds, this coating revealed a higher critical potential for oxidation film destruction. The results of this research collectively show that regulating the microstructures of laser-clad coatings by applying different scanning speeds is a feasible strategy to optimize the wear resistance of the coatings under corrosion.