Using the electrosorption technology treatment the cyanide wastewater has a good treatment effect, but the mechanism is not completely clear. In this paper, we conducted electrosorption experiments using simulated cyanide solutions to study the adsorption kinetics, thermodynamics, adsorption isotherms and analyze the reaction mechanism of zinc-cyanide and copper–cyanide complex ions. The results show that the electrosorption process of weak metals cyanide complexes treated by coal-based (CB) electrode conforms to the second-order kinetic model and follow the Langmuir model, affected by the dipole force and exchange of coordination groups. The equilibrium adsorption amounts of the two species at 2 V were 1.53 and 1.74 times higher than those at open circuit, respectively. During the electrosorption process, affected by the pseudo-capacitance, pore structure of CB electrodes and the charges of complex ions, the zinc-cyanide complex is bound in the double electric layer on the anode surface by the electric field, but partly decomposed to produce zinc ions and forms Zn(OH)2 in alkaline solution then generates ZnO precipitates, a small amount of Zn2+ were electrostatically adsorbed on the cathode surface for reduction deposition. However, the majority of the copper–cyanide complexes were purified by electrostatic adsorption to the double layer near the anode, while a small amount of decomposition occurred to produce Cu(OH)2 in the alkaline system, and almost no copper was deposited by reduction. This research results can enable us to better understand the removal characteristics of the weak metal cyanide complex ions in the process of electrosorption by CB electrode, and have great significance for the application of electrosorption technology to the treatment of cyanide wastewater.