A simple hard template method and hydrothermal process have been employed to fabricate a self-standing hierarchical porous MnO2/graphene film. Thus-constructed electrode materials for binder-free supercapacitors exhibit a high specific capacitance of 266.3 F g(-1) at the density of 0.2 A g(-1). Moreover, the two-electrode device demonstrates an excellent rate capability and cycling stability with capacitance retention of 85.1% after 2000 charge-discharge cycles at a current density of 1 A g(-1). The porous nano-structured design can effectively improve the specific surface areas and account for the shorter relaxation time for the electrodes, resulting in a high electrochemical performance. (c) 2014 Elsevier Inc. All rights reserved.