As candidates of the next generation batteries, aqueous zinc-ion batteries (ZIBs) have drawn widespread attention owing to the advantages of environmental friendliness, low cost and ultrahigh theoretical capacity. In order to obtain superior zinc ions (Zn2+) storage ability, the cathode materials with eminent electrochemical property are placed great expectations. Herein, the hierarchical 3D a-V2O5@Ti3C2Tx microsphere is prepared by a simple spray drying process. In the heterostructure, the amorphous V2O5 not only endows abundant active sites for Zn2+ storage but also effectively alleviates Ti3C2Tx MXene nanosheets restacking. Meanwhile, the presence of conductive Ti3C2Tx MXene framework significantly enhances the conductivity and reaction kinetics of the electrode material. As a result, the 3D a-V2O5@Ti3C2Tx exhibits an impressive Zn2+ storage ability, including the high reversible capacity (604 mAh g−1 at 0.5 A g−1), the superior rate performance and the splendid cycling stability. Furthermore, the relevant mechanism is illustrated via various characterizations. Moreover, the as-fabricated pouch ZIBs based on the 3D a-V2O5@Ti3C2Tx displays a potential practical application prospect as flexible energy storage devices. Hence, this work may provide an inspiration for the rational design of high performance ZIBs cathode materials.