Cobalt vanadate (Co3V2O8, CVO) nanowires assembled by nanosheets are successfully synthesized using a two-step hydrothermal method. Annealing temperatures can alter the specific surface area of the CVO samples. The physicochemical and electrochemical properties of these CVO samples are systematically characterized and compared. Impressively, the as-prepared CVO exhibits a higher reversible specific capacity and better rate performance than other annealed CVO electrodes, including a specific capacity of 1810 mAh g–1 at 200 mA g–1 over 50 cycles. Density functional theory computations indicate that the binding energy of CVO decreases after adsorbing Li atoms, leading to a high pseudocapacitance contribution of the electrodes.