We select iron as the anode and nickel as cathode. Sodium hydroxide solution is used as electrolytic solution in the electrochemical process to generate a strong oxidizing substance and react with organic sulfides. Comparing with other oxidizing reagents, it has highly efficient reactive oxidation products and deep desulfurization realization. Kerosene with a S content of 180.0 ppmw was directly used, and a constant current of 500 mA was proposed in this work. The concentration of NaOH, reaction temperature, time, ratio of solution and kerosene, and selection of extraction agents were all discussed. This method has a good effect on the removal of organic sulfide in kerosene, and the desulfurization efficiency achieves 91.26%. Furthermore, the analysis results of GC FPD, GC MS, and FTIR demonstrated that the 1-heptanethiol in model oil could be effectively oxidized under the optimal desulfurization conditions. Finally, the desulfurization mechanism of this kind of electrochemical oxidation is proposed, which is based on the results of our experiments.