The Co 3 O 4 nanowires@MnO 2 nanolayer or nanoflakes core–shell arrays (Co 3 O 4 @MnO 2 nanolayer or nanoflakes NWAs) supported on carbon fiber paper have been fabricated via a facile and green method and further investigated on the performance as the electrodes for supercapacitors. Our experimental results evidently indicate that both the Co 3 O 4 @MnO 2 nanoflakes and nanolayer NWAs are capable of delivering specific capacitances as high as 1209.4 and 1215.6Fg −1 (based on the MnO 2 ) at the current density of 1Ag −1 . Due to the delicately designed hierarchical nanostructure that distributing the nanoscaled MnO 2 on the nanowires with better electric conductivity, the active materials take advantage of the high effective surface area, facile electrolyte diffusion and fast electron transfer. The phenomenon that the Co 3 O 4 @MnO 2 nanolayer NWAs with smaller specific surface area become superior in electrochemical performance to the Co 3 O 4 @MnO 2 nanoflakes NWAs has been carefully investigated. The smaller charge transfer and electrolyte diffusion resistances are mainly demonstrated to be responsible. The analyses presented here could contribute to developing the optimal nanostructure of electrode materials for high-performance supercapacitors.