This study presents a novel approach to enhance the performance of low-temperature aqueous zinc batteries (LT-ZIBs) by introducing delocalized electrons through intrinsic defect engineering in the cathode material. The researchers fabricated oxygen-deficient V₂O₅ supported on hierarchical porous carbon (ODVO@HPC) to accelerate the desolvation of Zn(H₂O)₆²⁺ ions and promote the reversible transport of Zn²⁺ across the electrolyte/cathode interface. The ODVO@HPC electrode exhibits superior electrochemical performance, including high capacity robustness from 25 to −20°C, a capacity of 470 mAh g⁻¹ at −20°C, and a long lifespan of 50,000 cycles. The enhanced performance is attributed to the formation of delocalized electrons, which reduce the desolvation barriers and improve the diffusion kinetics of Zn²⁺ ions. The study demonstrates the potential of this defect engineering strategy to achieve high-performance LT-ZIBs with improved low-temperature performance and long cycle life.This study presents a novel approach to enhance the performance of low-temperature aqueous zinc batteries (LT-ZIBs) by introducing delocalized electrons through intrinsic defect engineering in the cathode material. The researchers fabricated oxygen-deficient V₂O₅ supported on hierarchical porous carbon (ODVO@HPC) to accelerate the desolvation of Zn(H₂O)₆²⁺ ions and promote the reversible transport of Zn²⁺ across the electrolyte/cathode interface. The ODVO@HPC electrode exhibits superior electrochemical performance, including high capacity robustness from 25 to −20°C, a capacity of 470 mAh g⁻¹ at −20°C, and a long lifespan of 50,000 cycles. The enhanced performance is attributed to the formation of delocalized electrons, which reduce the desolvation barriers and improve the diffusion kinetics of Zn²⁺ ions. The study demonstrates the potential of this defect engineering strategy to achieve high-performance LT-ZIBs with improved low-temperature performance and long cycle life.