The introduction of different ions is an effective method for regulating electron distribution and increasing the electrocatalytic activity of spinel cobalt sulfide (Co3S4). However, the effect of doping different ions on water splitting performance has not been systematically clarified. Therefore, a detailed research is done to illuminate the doping of different ions on the water splitting performance of spinel cobalt sulfide MCo2S4 (M = Ni, Cu and Co) nanorods grown on Ni foam. To drive the electrocatalytic current of 50 mA/cm(2) and 10 mA/ cm(2), the CuCo2S4/NF material only requires an overpotential of 240 mV for oxygen evolution reaction (OER) and an overpotential of 142 mV for hydrogen evolution reaction (HER). The results of density functional theory and experiment demonstrate that the strong water adsorption energy and the large electrochemical activity area make CuCo2S4/NF show good catalytic activity. The CuCo2S4/NF nanorods material presents superior electrochemistry performance with a small voltage 1.53 V. The water oxidation activity increases linearly before nonlinearly improving with the increasing of pH, indicating that the substrate changes from water to hydroxyl. It is noteworthy that CuCo2S4/NF will be transformed into amorphous oxide active species, which will act as a stable catalyst during the reaction. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.