Vanadium pentoxide is emerging as a low-cost and high-performance pseudo-capacitive electrode material but suffers from poor stability. Herein, we demonstrate that the electrochemical performance and stability of V2O5 nanowires can be significantly improved by coating a thin carbon layer as shell. Our study shows that the V2O5@C core shell nanowires achieve a remarkable areal capacitance of 128.5 F cm−2 at 10 mV s−1 with excellent rate capability. More than 94.4% of the initial capacitance is retained after 10,000 cycles for V2O5@C core shell nanowires, which is much higher than the pristine V2O5 nanowires (13.3%). This method could be extended to improve the stability and electrochemical properties of other electrode materials.