A facile template-free synthesis strategy is demonstrated to fabricate nanostructured NiO/N-doped graphene hybrid, in which NiO hollow nanospheres with hierarchically mesoporous structure are tightly anchored on N-doped graphene matrix. The mesoporous shell of NiO can not only provide sufficient electrode/electrolyte contact areas to accelerate ion diffusion and electron exchange, but also efficiently mitigate the volume change that occurs during long-time reactions. Simultaneously, the reduced graphene oxide with doping nitrogen atoms are employed as effectively conductive backbone, further enhancing the electrochemical performances. When used as anodic material for lithium ion batteries, the synergistic system delivers a reversible capacity up to 1104.6 mAh g(-1) after 150 cycles at a current density of 0.08 A g(-1) and 422.3 mAh g(-1) at a high charging rate of 4 A g(-1), which is better than those of the bare counterparts and most other NiO-based materials reported in the previous literatures. The hierarchically hollow NiO nanostructure combined with N-doped graphene matrix provides a promising candidate applied in advanced anode materials for lithium ion batteries. (C) 2017 Elsevier B.V. All rights reserved.