Although graphene oxide (GO) can be well dispersed in aqueous solution, direct reduction of GO in solution usually results in irreversibly precipitated agglomerates due to strong pi-pi interactions. Such a problem could be avoided by preparing layered graphene-based materials using an electrostatic spray deposition (ESD) technology. A composite film consisting of NiO nanograins@reduced graphene oxide nanosheets (NiO@rGO) with layered structure was realized by a facile one step binder-free ESD approach. It was deposited directly onto the nickel foam and showed excellent electrochemical capacitor properties, about 881 F g(-1) at a current density of 0.5 Ag-1 and 667 F g(-1) at 50 A g(-1) with an excellent cycling ability. Furthermore, this technique opens a new access to the preparation of layered graphene based composites with novel structures and properties. (C) 2014 Elsevier Ltd. All rights reserved.