High chromium cast iron (HCCI) has been widely used as wear-resistant material in the industry. Alloying is an effective way to improve the microstructure and mechanical properties of HCCI. This paper added multi-component V-Fe-Ti-Nb-C-Zr-B alloy (VFC) to HCCI, showing a significant synergistic solution-strengthening effect. The results show that the added V-Ti-Nb-B are dissolved in M7C3carbide to form the (Cr, Fe, V, Ti, Nb)7(C, B)3alloy carbide, and a small amount of V and all Zr are dissolved in austenite and martensite. Adding VFC into HCCI improved the hardenability of HCCI, decreased the residual austenite content from 6.0 wt% to 0.9 wt%, increased the martensite content from 70.7 wt% to 82.5 wt%, and changed the structure and content of M7C3carbide. These changes increased the hardness of as-cast and heat-tread HCCI by 1.4% and 4.1%, increased the hardness of austenite and martensite by 7.9% and 7.0%, increased the impact toughness by 16.9%, and decreased the friction coefficient and wear loss by 2.3 % and 7.0 %, respectively. Thus, the hardness, toughness, wear resistance, and friction resistance of HCCI alloy are improved simultaneously.