Since electrocatalytic oxygen evolution (OER) is a four-electron transfer reaction with very slow kinetics, there is great competition to develop cheap, durable and efficient catalysts for oxygen evolution. A molecular model is designed for density functional theory (DFT) simulation calculations to guide the experiment, and this hypothesis is fully supported by the experimental data. Herein, regulating the composition and morphology of the bimetallic VCo and MoCo sulfide and monometallic sulfide nanoparticles (NPs) at the oil-water interface was achieved via a one-step hydrothermal method for efficient and durable OER electrocatalysts. Compared to CoS and MoCoS, the VCoS NPs show superior OER performance. By adjusting the atomic composition ratio of the VCoS nanoparticles, the VCoS NPs (1 : 2 : 1.5 mole ratio) showed a significant OER overpotential η = 255 mV (10 mA cm-2), and their outstanding stability was demonstrated after 48 h of continuous testing. The CoS and MoCoS NPs were also tested for comparison. Density functional theory (DFT) calculations showed that appropriate V doping (VCoS) can heighten the density of states (DOS) of the Fermi level, which generates more charge density and reduces the intermediate adsorption energy. This study not only provides efficient and powerful integrated catalysts, but also details a DFT calculation model guided by experiments to regulate the oxygen insertion technology, thus leading to the design of ideal materials and enabling more far-reaching applications in electrocatalysis.