This study fabricates wear-resistant composite layers (WRCLs) strengthened with in situ vanadium carbide (VC) ceramics on the surface of carbon steel via casting infiltration technology. The abrasive and impact wear properties are evaluated accordingly. The action mechanism of VC ceramics of different scales in the wear process is clarified. The VC ceramics used in WRCLs include microscale primary VC and nanoscale secondary VC. Vanadium content exerts a considerable effect on the wear resistance of composite layers. The optimal vanadium contents for resisting abrasive and impact wear are 5.5 wt% and 5.1 wt%, respectively. The abrasive and impact wear resistance of the WRCLs are 2.5 and 1.9 times that of Cr20 cast iron as the vanadium content reaches the optimal amount. The improved wear resistance of the WRCLs is attributed to the synergy of the dual-scale VC ceramics. The microscale VC ceramics resist scratch efficiently while the nanoscale VC ceramics strengthen the matrix. Therefore, dual-scale VC ceramics work synergistically to reduce wear.