A graphene/NiO composite was prepared by simple chemical precipitation followed by thermal annealing. The results of XRD, FT-IR, FE-SEM, FE-TEM, and EDS analyses confirmed the presence of NiO nanoparticles with plate structure on the graphene surface. The discharge capacities of graphene, graphene/NiO (37wt.%), and graphene/NiO (59wt.%) are about 302, 604, and 856mAhg−1 at 5000mAg−1 (5C), respectively. The cells containing 59wt.% NiO show the best performance, and the graphene nanocomposite materials have high rate properties that are comparable to some of the best results reported in the literature using NiO. This graphene/NiO (37 and 59wt.%) nanocomposite displays superior LIB performance with large reversible capacity, high Coulombic efficiency, good cyclic performance, and excellent rate capability, highlighting the importance of the anchoring of nanoplate structure NiO on graphene sheets for maximum utilization of electrochemically active graphene/NiO for energy storage applications in high-performance LIB.