 In spite of the high capacity of 978 mAh g−1, the practical application of zinc oxide (ZnO) electrode is limited by its unsatisfactory electrochemical performance caused by the low intrinsic electrical conductivity and large volume changes during the alloying/dealloying process. To overcome this problem, ZnO nanoparticles are uniformly attached on nickel foam via a simple solvothermal method with graphene as morphology-controlling agent (G–ZnO/Ni). Experimental results show that the ZnO nanoparticles were uniformly dispersed on the nickel foam in monolayer with obvious clearance formed between ZnO nanoparticles, which could help to accommodate the volume change and provide enough adhesive force to stabilize the ZnO nanoparticles, thus improving the cycling stability. Moreover, the as-prepared composites can be directly used as the binder-free electrodes for LIB anode and exhibit good performance in lithium storage with high reversible capacity and excellent cycling stability with a retained capacity of 537 mAh g−1 after 1600 cycles at a current density of 600 mA g−1.