In this study, we demonstrated the co-modification of oxygen vacancies and heterojunctions in VO₂(B) (V_O–VO₂/MXene) as a cathode material for zinc-ion batteries (ZIBs). VO₂ nanobelts are uniformly distributed on MXene nanosheets, which providing complete electron transport channels during the insertion or de-insertion of Zn²⁺. The formation of oxygen vacancies provides additional active sites and enhances the conductivity of VO₂. Density functional theory calculations reveal that the oxygen vacancies effectively facilitate reversible intercalation/deintercalation process, which results in rapid intra-crystal zinc ion diffusion. The combination of V_O–VO₂ with MXene introduces an interfacial electric field, ultimately leading to synergistic enhancement in electrochemical activity. The V_O–VO₂/MXene composite exhibits the highest specific capacity (287 mAh g⁻¹) at 10 A g⁻¹ and excellent cycling lifespan (253 mAh g⁻¹ after 3000 cycles) for ZIBs. This work provides a reliable strategy for the co-modification of metal oxide electrodes with oxygen vacancies and heterostructures.