In this work, an effective and facile strategy to fabricate binder-free electrodes composing 3D graphene network (3DGN) and octahedral CuO has been proposed. In this design, Cu-based MOF crystals were first uniformly grown on the surface of 3DGN substrate through a solution immersion method and then a subsequent thermal treatment isolated the formation of well-dispersed nanostructured CuO octahedras wrapped 3DGN. The obtained 3DGN/CuO composites were utilized as binder-free anodes of lithium ion batteries for the first time, yielding a high reversible gravimetric capacity of 409 mAh g(-1) (a large areal capacity of 0.39 mAh cm(-2)) at 100 mA g(-1), excellent cyclability with 99% capacity retention after 50 cycles and superior rate capability of 219 mAh g(-1) at 1600 mA g(-1). The remarkable performance of the composite electrode can be reasonably attributed to the synergistic interaction between octahedral CuO nanoparticles with high capacity and the conductive 3D graphene network with a large surface area and an interconnected porous structure. (C) 2016 Elsevier B.V. All rights reserved.