A high-vanadium alloy composite layer was prepared on the surface of a carbon steel using cast composite technology, and the wear properties of the composite layer were investigated. The results showed that the microstructure of the composite layer was composed of primary vanadium carbides (VC), flake martensite, residual austenite, and fine VC. The hardness of the cast alloy layer was 63 HRC. The abrasive wear resistance and impact wear resistance were increased by 60% and 26%, respectively, compared with those of high-chromium cast iron. The excellent wear resistance of the cast alloy layer is attributed to the high-hardness primary vanadium carbide and the large number of fine secondary vanadium carbides precipitated out of the cast alloy layer.