The electrochemical removal (ECR) of water pollutants by activated carbon fiber (ACF) electrodes from wastewater was investigated over wide range of electrochemical reaction time. The ECR capacities of ACF electrodes were associated with their internal porosity and were related to physical properties and to reaction time. And, surface morphologies and elemental analysis for the ACFs after electrochemical reaction are investigated by SEM and EDX to explain the changes in adsorption properties. The FT-IR spectra of ACFs for the investigation of functional groups show that the electrochemical treatment is consequently associated with the homogeneous removal of pollutants with the increasing surface reactivity of the activated carbon fiber surfaces. The ACFs were electrochemically reacted to waste water to investigate the removal efficiency for the COD, T-N and T-P. From these removal results of pollutants using ACFs substrate, satisfactory removal performance was obtained. The outstanding removal effects of the ACFs substrate were determined by the properties of the material for adsorption and trapping of organics, and catalytic effects.