In this paper, ZnCo2O4 nanowire arrays with a uniform carbon coating were introduced when polyvinyl alcohol (PVA) served as the carbon source. The coating process was completed by a facile bath method in PVA aqueous solution and subsequent pyrolyzation. The PVA-derived carbon-coated ZnCo2O4 nanowire array composites can be used directly as the binder-free and self-supported anode materials for lithium-ion batteries. In the carbon-coated ZnCo2O4 composites, the carbon layer carbonized from PVA can accelerate the electron transfer and accommodate the volume swing during the cycling process. The lithium storage properties of the carbon-coated ZnCo2O4 composites are investigated. It is believed that the novel carbon-coating method is universal and can be applied to other nanoarray materials.