Herein, we report preparation of a novel ordered mesoporous carbon/reduced tungsten oxide nanocomposite by post-addition into the ordered mesoporous carbon prepared by triconstituent co-assembly method. The as-prepared composite material is characterized using various analysis methods and nitrogen sorption isotherms, which reveal that small mesopores located within pore wall are selectively filled by tungsten oxide and also reduced tungsten oxide crystals with size of 6 nm are uniformly dispersed in the carbon matrix. Hence, our prepared nanocomposite possesses an ordered pore structure optimized for fast electrolyte transport and highly accessible charge storage sites. When applied as supercapacitor electrode, it exhibits a high volumetric capacity (125Fcm−3), an excellent rate capability (79%) and capacitance increase after long-term cycles (113%).