Three distinct operational conditions, namely, ohmic, limiting current, and electroconvection region, respectively, can be created by applying different electric fields during ED operations. The fundamental of cation transport under ohmic and limiting current is well understood, however, the mechanism on cation transport under electroconvection is unclear. In order to clarify the feasibility of operating ED under electroconvection for the treatment of industrial wastewater (copper ion as the target pollutant), the methods of current-voltage profiling (C-V curve) and electrochemical impedance spectroscopy (EIS) were used to study the transport characteristics of Cult through a cationic exchange membrane (CEM). The relevant operational parameters obtained above under electroconvection conditions were applied to a continuous ED system as to investigate the removal efficiency of Cu2+-containing wastewater. Results indicated that ED system operated under electroconvection conditions was able to achieve high Cu2+ removal efficiency (around 74% in 4-min treatment) at high electricity efficiency as the theoretical calculation (based on Cu2+ transport number close to 1.0). The pH of copper wastewater in the ED system decreased slightly from 4.7 to 4.0 under electroconvection operation. The interface at the membrane-water was perturbed by the electroconvection operation, which facilitated ions transport across the membrane. An equivalent circuit composed of the Rs, Cm and Rm (parallel circuit representing the CEM), and constant phase element described well the Cu2+ transport behavior in the membrane solution system according to the p value is greater than 1.0. (C) 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.