The NiO/graphene (NiO/G) composite nanofibers were successfully synthesized by simple electrospinning followed by heat treatment. They as anode materials for lithium ion batteries demonstrated the more outstanding electrochemical performance when compared with the NiO + Ni composite nanofibers as the reference. NiO/G exhibited a higher discharging/charging capacity (about 712 mAhg(-1) at the third cycle) with a coulombic efficiency of nearly 100% than NiO + Ni (547 mAhg(-1)). NiO/G also demonstrated the excellent cycling stability due to its higher discharging capacity of 571 mAhg(-1) and retention rate of 78% than NiO + Ni (184 mAhg(-1) and 33%) when subject to 50 cycles at 100 mAg(-1). Moreover, its rate performance was also greatly improved when compared with NiO + Ni owing to its higher discharging capacity (305 mAhg(-1), 556 mAhg(-1)) and retention rate (44%, 80%) at the current density increased from 100 mAg(-1) to 2000 mAg(-1), and then recovered to 100 mAg(-1). The outstanding electrochemical performance of the NiO/G electrode is closely related to its lower ohmic resistance (2.1 omega)/charge transfer resistance (86.5 omega), and stronger diffusion capability of Li+ resulting from the high specific surface area, excellent conductivity and a certain charge storage capacity of graphene.