Replacing oxygen evolution reaction (OER) by ethanol oxidation reaction (EOR) is an effective strategy to reduce energy consumption in water splitting. Thus, a heterostructure composed of NiO nanosheets and CeO2 nanorods (NRs) (NiO@CeO2) are preapred by hydrothermal method as an efficient electrocatalyst for EOR. Characterization and electrochemical results suggest that NiO@CeO2 shows enhanced EOR performance due to the synergistic effect, which deliver current density (j) of 10 mA cm-2 at only 1.37 V, much smaller than that of NiO and CeO2. So, NiO@CeO2-based electrode shows a low cell voltage (1.39 V@ 10 mA cm-2) for overall water splitting (OWS).