Adsorption and electrosorption of copper ions (Cu 2+ ) from wastewater were investigated with variously modified activated carbon fiber (ACF) cloth electrodes. Commercial polyacrylonitrile-based ACF cloths were modified by nitric acid or impregnated with chitosan solution. The surface characteristics of ACFs before and after modification were evaluated by nitrogen adsorption–desorption isotherms, zeta potential, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry. Adsorption and electrosorption capacities of Cu 2+ on ACF cloths without and with a bias potential were measured, respectively, and the electrosorption isotherms were also investigated. The initial pH of the copper ion solution was adjusted to 4.0. Experimental results showed that electrosorption effectively increases adsorption capacity. The adsorption/electrosorption isotherms of Cu 2+ on ACF cloths were in good agreement with Langmuir and Freundlich equations. The equilibrium adsorption capacity at 0.3V was 0.389mmol/g, which is two times higher than that at open circuit. The maximum electrosorption capacity of Cu 2+ on chitosan impregnated ACF cloths was 0.854mmol/g, which is about 2.2 times higher than that on the pristine cloths.