A NiO–graphene hybrid film with 3D hierarchically porous structure has been rationally designed and constructed through a series of controlled fabrication processes. Multilayered porous graphene sheet network with the pore size of several micrometers is created via a so-called “on-water spreading” method, which is facile, economical, efficient and scalable. Then, the cross-like NiO nanoflakes film is uniformly grown onto the porous graphene sheet framework by a chemical bath deposition. The NiO–graphene hybrid film exhibits specific capacitance of 540 F g−1 at 2 A g−1 with 80% capacitance retention after 2000 cycles in 2 M KOH aqueous solution, which is much higher than that achieved from the bare NiO nanoflakes film (370 F g−1, with 66% capacitance retention). Moreover, chronoamperometry and electrochemical impedance spectroscopy measurements reveal that the NiO–graphene hybrid demonstrates enhanced reaction kinetics with about only 50% of respond time for NiO/NiOOH reaction and 79% of charge-transfer resistance compared with those of the bare NiO film. The proposed strategy could offer an effective way to fabricate graphene-based electrode materials for applications in various energy-storage devices.