MnO2 with urchin-like nano/micro hierarchical architecture was synthesized through an easy hydrothermal method at low temperature and used to prepare MnO2/graphene hybrid composite as electrode materials through an easy and efficient solution-based method. The MnO2 particles in the composite with 66.7% mass ratio could achieve specific capacitance as high as 451.5 F g(-1) at a scan rate of 10 mV s(-1) and exhibit good cycle stability with 93.8% capacitance retention over 2000 cycles. These properties result from the unique urchin-like nano/micro hierarchical structure of MnO2 as well as the function of graphene in enhancing the conductivity and utilization of MnO2.