A two-dimensional MXene (Ta4C3) was innovatively used herein to modulate the space group and electronic properties of vanadium oxides, and the MXene/metal–organic framework (MOF) derivative VO2(B)@Ta4C3with 3D network cross-linking was prepared, which was then employed as a cathode to improve the performance of aqueous zinc ion batteries (ZIBs). A novel method combining HCl/LiF and hydrothermal treatments was used to etch Ta4AlC3to obtain a large amount of accordion-like Ta4C3, and the V-MOF was then hydrothermally grown on the surface of the stripped Ta4C3MXene. During the annealing process of V-MOF@Ta4C3, the addition of Ta4C3MXene liberates the V-MOF from agglomerative stacking, allowing it to show additional active sites. More significantly, Ta4C3prevents the V-MOF in the composite structure from converting into V2O5of space group Pmmnbut into VO2(B) of space group C2/mafter annealing. A considerable advantage of VO2(B) for Zn2+intercalation is provided by the negligible structural transformation during the intercalation process and the special tunnel transport channels, which have an enormous area (0.82 nm2along the baxis). According to first-principles calculations, there is a strong interfacial interaction between VO2(B) and Ta4C3, which deliver remarkable electrochemical activity and kinetic performances for the storage of Zn2+. Therefore, the ZIBs prepared with the VO2(B)@Ta4C3cathode material exhibit an ultra-high capacity of 437 mA h·g–1at 0.1 A·g–1while showing good cycle performance and dynamic performance. This study will offer a fresh approach and a reference for creating metal oxide/MXene composite structures.