A research article presents a novel strategy for enhancing the performance of low-temperature aqueous zinc (LT-ZIBs) batteries by utilizing intrinsic defect engineering in cathode materials to achieve fast interfacial electrocatalytic desolvation. The study focuses on the development of an oxygen-deficient vanadium pentoxide (ODVO) supported on hierarchical porous carbon (HPC), denoted as ODVO@HPC. This material is designed to facilitate the rapid dissociation of the solvated Zn²+ ions, enabling efficient diffusion and insertion/extraction processes. The ODVO@HPC electrode demonstrates exceptional performance, maintaining high capacity and stability across a wide temperature range, including -20°C. At -20°C, the ODVO@HPC electrode delivers a capacity of 191 mAh g⁻¹ at 50 A g⁻¹ and lasts for 50,000 cycles, significantly outperforming previous reports. The study also highlights the effectiveness of delocalized electrons in the cathode, which enhance the desolvation process and improve the kinetics of Zn²+ ion transport. The results demonstrate that the ODVO@HPC cathode provides a record-level lifespan and high-rate performance, making it a promising candidate for practical low-temperature zinc batteries. The research underscores the importance of defect engineering in achieving efficient and stable zinc-ion storage and transport in aqueous electrolytes.A research article presents a novel strategy for enhancing the performance of low-temperature aqueous zinc (LT-ZIBs) batteries by utilizing intrinsic defect engineering in cathode materials to achieve fast interfacial electrocatalytic desolvation. The study focuses on the development of an oxygen-deficient vanadium pentoxide (ODVO) supported on hierarchical porous carbon (HPC), denoted as ODVO@HPC. This material is designed to facilitate the rapid dissociation of the solvated Zn²+ ions, enabling efficient diffusion and insertion/extraction processes. The ODVO@HPC electrode demonstrates exceptional performance, maintaining high capacity and stability across a wide temperature range, including -20°C. At -20°C, the ODVO@HPC electrode delivers a capacity of 191 mAh g⁻¹ at 50 A g⁻¹ and lasts for 50,000 cycles, significantly outperforming previous reports. The study also highlights the effectiveness of delocalized electrons in the cathode, which enhance the desolvation process and improve the kinetics of Zn²+ ion transport. The results demonstrate that the ODVO@HPC cathode provides a record-level lifespan and high-rate performance, making it a promising candidate for practical low-temperature zinc batteries. The research underscores the importance of defect engineering in achieving efficient and stable zinc-ion storage and transport in aqueous electrolytes.