CrFeNiCoMnMo_0.5 and CrFeNiCoMn high-entropy alloy (HEA) coatings were successfully prepared on the surface of automotive steel using laser coating technology. The influence of Mo addition on the microstructure, phase composition, crystallographic properties, nanoindentation characteristics, and wear behavior of the coatings was systematically investigated. The results revealed that the CrFeNiCoMnMo_0.5 HEA coating comprised an FCC phase and a σ phase. The incorporation of Mo increased lattice distortion within the FCC phase, enhancing its solid solution strengthening effect. Consequently, the nano-hardness of the CrFeNiCoMnMo_0.5 coating was significantly improved, reaching 7.81 GPa± 0.13 GPa, which was markedly higher than that of the CrFeNiCoMn coating. Additionally, the CrFeNiCoMnMo_0.5 coating exhibited higher H/E and H³/E² ratios, signifying exceptional resistance to plastic deformation. The enhanced nano-hardness resulted in superior wear resistance, with an average friction coefficient of 0.48 and a specific wear rate of 2.307×10^-6 mm³/(N·m). The primary wear mechanisms were identified as abrasive wear, adhesive wear, and surface fatigue wear. This study underscores the critical role of Mo in improving the mechanical and wear properties of high-entropy alloy coatings for automotive applications.