Abstract: To reveal the influence mechanism of electrochemical modification on the floatability of calcium ion activated muscovite, the calcium chloride solution was electrolytically modified and the pure mineral flotation test of muscovite was carried out. Based on this, muscovite samples were characterized by infrared spectroscopy, photoelectron spectroscopy and Zeta potential. The results showed that compared with the unmodified, the recovery rate of muscovite decreased from 62.10% to 49.00% after electrochemical modification of Ca²⁺ ion, which reduced the activation ability of Ca²⁺ ion on muscovite floatability to a certain extent. The mechanism of electrochemical modification weakens the ability of Ca²⁺ ion to activate muscovite lies in that electrochemical modification can promote the degree of hydrolysis reaction of Ca²⁺ ion in solution and generate micro-solution Ca(OH)₂. Calcium hydroxide reacted with oleic acid in the pulp, induced the decrease of the content of both the oleic acid and oleic acid ion in the pulp, meanwhile, reducing the reaction probability of Al of active point on muscovite surface with other ions such as oleic acid. In addition, electrochemically modified Ca²⁺ ion can negatively increase the Zeta potential of muscovite surface, which is not conducive to the physical adsorption of oleic acid ions in the local positive region on the muscovite surface, and ultimately weakens the activation of Ca²⁺ ion on the floatability of muscovite. The study provides reference significance for improving the separation effect of muscovite-containing non-metallic minerals.