To satisfy the urgent requirements for developing high-performance electrode materials for aqueous copper batteries, vanadium-based Prussian blue analogue ferrocyanide vanadium (VHCF) was fabricated by a simple co-precipitation method and utilized as cathodes for aqueous copper batteries. The effects of reaction temperature and stirring speed on the micromorphology and microstructure of VHCF samples were discussed, while the differences in electrochemical performances of different VHCF samples were investigated, and the copper storage mechanisms of VHCF samples were analyzed. The results revealed that the rich [Fe(CN)6]4-, small particles and stable structure of cubic VHCF could be obtained by ascending the reaction temperature and stirrer speed. The more [Fe(CN)6]4- could provide more chemical active sites for Cu2+ ions, the smaller particle could improve the Cu2+ ions diffusion rate, and the more stable crystalline water combined with the Prussian blue framework could improve the cycling stability. The Cu2+ ions displaced the V5+ ions in the VHCF framework to form an irreversible new phase during the electrochemical processes. VHCF cathodes delivered a high initial discharge specific capacity of 146.5 mA·h/g at a current density of 0.1 A/g and retained a reversible capacity of 56.1 mA·h/g after 500 cycles, and exhibited the discharge specific capacity of 60.1 mA·h/g at a high current density of 1.0 A/g. Therefore, the applications of VHCF in aqueous copper batteries provide new possibilities for the design and development of high-performance electrode materials for aqueous copper ion batteries.