In this study, the MnO2/reduced graphene oxide/Ni (MnO2/rGO/Ni) composite foam as a binder-free supercapacitor electrode was prepared by a facile method. The rGO film has been firstly coated on the skeletons of Ni foam current collectors by chemical deposition method and that have been used as substrates for preparation of a novel three dimensional rGO/Ni composite foam-supported porous MnO2 film by the hydrothermal method. The structure of MnO2/rGO/Ni composite foam was characterized by Raman spectra, IR spectra and Scanning electron microscopy. It indicated that the high-quality rGO film have been coated on skeletons of Ni foam current collectors and the MnO2 film had a 3D network microstructure, consisting of interlaced nanosheets. Furthermore, the binder-free MnO2/rGO/Ni composite foam electrode has been characterized by the cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectra. It exhibited excellent pseudocapacitive behavior with specific capacitance of 479.0 F/g. The capacitance could retain about 83.5% after 1000 charge–discharge cycles. This simple synthetic approach provides a convenient route for the large scale preparation of 3D porous MnO2/rGO/Ni composite foam for lots of applications in future.