The metal oxides/titania nanotubes composite electrode materials have been employed as an efficient strategy to achieve enhanced electrochemical performance. However, the conventional closed-packed nanotubes structure allows few secondary decorations which can not make full use of its characteristics and thus limit the performance of supercapacitors. In this work, spaced TiO2 nanotube arrays were employed as a substrate for the electrodeposition of nanocrystalline MoO3 to synthesize composite electrode material for high performance supercapacitor applications. The results demonstrate that a very high specific capacitance (127.71 mF/cm2) at a current density of 0.6 mA/cm2 in 2 M aqueous Li2SO4 solution and good capacitance behavior even after 3000 continuous charge–discharge cycles, suggesting promising applications as an electrode material for supercapacitors.