A facile strategy is developed for the synthesis of hierarchical polyaniline nanowires/ordered bimodal mesoporous carbon (PANI/OBMC) composites via chemical oxidative polymerization. Structural and morphological characterizations indicate that the polyaniline nanowire arrays with 20–30 nm diameters are grown on the surface of the OBMC. The bimodal pore distribution and hierarchical nanostructure endow the PANI/OBMC composite with high surface area of 599 m2 g−1. Electrochemical performance of the hierarchical PANI/OBMC composite as supercapacitor electrode materials has been evaluated by cyclic voltammetry and galvanostatic charge–discharge techniques. The hierarchical composite with 60 wt% PANI possesses the highest specific capacitance of 517 F g−1 and outstanding cycling stability with a capacitance retention of 91.5% after 1000 cycles. The coexistence of primary mesopores and abundant small mesopores is in favor of the fast penetration of electrolyte and the unique hierarchical structure facilitates the ion diffusion and shortens the charge transfer distance, which lead to superior electrochemical performance of PANI/OBMC-60%.