Abstract: The pure mineral flotation experiment of muscovite was carried out by using citric acid before and after electrochemical pretreatment, and the samples were characterized by XPS, Zeta potential and FITR. On this basis, the mechanism of electrochemical pretreatment of citric acid and muscovite flotation behavior under the sodium oleate system was investigated. The results indicated that electrochemical pretreatment could improve the separation effect of citric acid on muscovite. The muscovite recovery of only 3.4% was obtained by the electrochemical pretreatment of the citric acid solution with the concentration of 2.38×10^-6 mol/L under the pulp condition of pH value of 7 and sodium oleate concentration of 9.20×10^-4 mol/L. The phenomenon that the citric acid can enhance the floatability of muscovite can be explained as follow:the electrochemical pretreatment can increase the degree of hydrolysis and ionization of citric acid. The adsorption of the C₆H₇O₇^- and C₆H₆O₇^2- on the surface of muscovite was enhanced, which correspondingly weakened the electrostatic adsorption of oleate on the surface of mica, resulting in the decrease in the floatability of muscovite. The study can provide a new idea to improve the separation efficiency of muscovite, and also provide a reference for the application of electrochemical pretreatment reagent in flotation.