Nickel oxide–polypyrrole (NiO–PPy) composites for lithium-ion batteries were prepared by a chemical polymerization method with sodium p-toluenesulfonate as the dopant, Triton-X as the surfactant, and FeCl3 as the oxidant. The new composite material was characterized by Raman spectroscopy, thermogravimetric analysis, scanning electron microscopy, and field-emission scanning electron microscopy. Nanosize conducting PPy particles with a cauliflower-like morphology were uniformly coated onto the surface of the NiO powder. The electrochemical results were improved for the NiO–PPy composite compared with the pristine NiO. After 30 cycles, the capacities of the NiO and the NiO–PPy composite were about 119 and 436 mAh·g−1, respectively, indicating that the electrochemical performance of the composite was significantly improved.