Abstract: The effect of the electrochemical treatment on the surface structure and flotability of the macerals in Shenmu coal was studied, which aimed to provide a theoretical foundation for the separation by electrochemical flotation. The influence of anode and cathode on the surface structure, surface potential and wettability of Shenmu vitrinite and inertinite was investigated. The results show that the electrochemical treatment has a significant effect on the oxygen-containing functional groups of coal macerals such as-OH, -COOH, etc. The surface zeta potential of macerals moves towards the electronegativity and the wettability of macerals increases when the treatment is conducted with electrochemical anode. However, the surface zeta potential of macerals moves towards the electropositivity and the wettability decreases when the electrochemical cathode is used. The variation trend of contact angle for the vitrinite treated with electrochemical anode is more obvious, while the inertinite treated with electrochemical cathode is more conspicuous.