Al2CrFeNiMoSix (x = 0, 0.25, 0.5, 0.75, 1.0) high-entropy alloy coatings were designed and fabricated on Cr12MoV by laser cladding, and the influence of Si on microstructure and wear resistance was investigated. The results show that Al2CrFeNiMoSi0 coating exhibits equiaxed crystal consisted of BCC phase. However, Al2CrFeNiMoSix (x = 0.25–1.0) coatings present Cr1.5Mo1.5Si besides of BCC phase, and the equiaxed crystal is significantly refined. Under the comprehensive effect of grain refinement strengthening and second-phase strengthening, the microhardness of Al2CrFeNiMoSix coatings is improved 152 ~ 234%, and the wear volume is reduced 59.7 ~ 78.3% compared with the substrate. Among them, Al2CrFeNiMoSi0.5 coating expresses the best wear performance. Al2CrFeNiMoSi0 coating has fatigue wear mechanism; however, Al2CrFeNiMoSi0.5 coating exhibits abrasive wear mechanism. Furthermore, the degree of oxidation wear decreases obviously with the increasing Si element.