Molybdenum is one of the valuable metals for the industry; its special properties make it extremely urgent to study the process of separation of molybdenum from other impurities. The article considers the optimization of electrochemical separation of molybdenum from Mo-W system. The electrochemical dissolution of molybdenum and tungsten in solutions of LiCl and NH4NO3 in dimethylsulfoxide was studied using polarization curves and calculation of the efficiency of anodic dissolution of molybdenum in the presence of tungsten. The electrolyte with a composition of 0.5 M LiCl; 5.2 M dimethylsulfoxide; 32.2 M water was selected as an effective solution for the electrochemical separation of molybdenum in the potential range of 1.0‒2.2 V. Results obtained in this study can be used for the development of selective separation method in the molybdenum production.