Composite electrodes based on vertically aligned multi-walled carbon nanotubes (MWCNTs) coated with vanadium oxide (V2O5) have used in supercapacitors. The vanadium (V) oxide (V2O5) cathodically deposited on titanium collector in vanadium oxide solution. The novel supercapacitor performed by V2O5/MWCNTs/Ti electrode in 1.0 M HCl aqueous solution can reach a specific capacitance of 713.3 F/g at 10 mV/s, which is larger than that of MWCNTs/Ti. To characterize the V2O5/MWCNTs/Ti composite electrode, cyclic voltammetry and galvanostatic charge-discharge method were executed, and the morphology of the composite electrode was examined by scanning electron microscope. This nanocomposite electrode greatly enhanced the utilization efficiency of supercapacitor electrode material, low material cost and provided both high capacitance and power density.