Vanadium‐based derivatives, featuring affordable cost and high theoretical capacity, have gathered widespread interest in the context of aqueous zinc‐ion batteries (ZIBs). However, the further application of vanadium‐based materials is hindered by the limited electrical conductivity and cycling lifespan. Herein, 1D chain‐like structure vanadyl ethylene glycolate (VEG, (VO(CH2O)2)), growing on the Ti3C2Tx MXene nanosheets, is synthesized via a one‐step oil‐bath heating process as cathode materials for ZIBs. Benefiting from the hybrid structure with high conductivity and abundant reactive sites, the VEG@MXene cathode exhibits a remarkable specific capacity (360.3 mAh g−1 at 0.5 A g−1), and impressive capacity retention (up to 85.2% after 3000 cycles at 10 A g−1). Mechanism analysis reveals a gradual phase transition from the original VEG on MXene to the stable Zn3V2O7(OH)2·2H2O nanoflakes accompanied by continuous zinc ion intercalation/deintercalation, offering more pathways for zinc ion transport. This work suggests that engineering conductivity‐enhanced vanadium‐based materials is a rational approach for developing promising cathode materials of ZIBs. A structure optimized composite, vanadyl ethylene glycolate@Ti3C2Tx MXene (VEG@MXene) via a one‐step oil‐bath heating approach is proposed as the cathode material for aqueous zinc‐ion batteries. With the MXene substrate enhancing the electrical conductivity and providing abundant reactive sites, the zinc//VEG@MXene batteries can deliver remarkable electrochemical performances.