The electro-chemical removal (ECR) of water pollutants by metal-ACF electrodes from wastewater was investigated over wide range of ECR time. The ECR capacities of metallic ACF electrodes were related to physical properties such as adsorption isotherm, surface area and pore size and to reaction time. Surface morphologies and elemental analysis for the metal supported ACFs after electro-catalytic reaction were investigated by scanning electron microscopy (SEM) and energy disperse X-ray (EDX) to explain the changes in adsorption properties. The IR spectra of metallic ACFs for the investigation of functional groups show that the electro-catalytic treatment is consequently associated with the removal of pollutants with the increasing surface reactivity of the activated carbon fibers. The metal-ACFs were electro-catalytically reacted to waste water to investigate the removal efficiency for the COD, T-N, NH4-N, NO3-N and NO2-N. From these removal results of the piggery waste using metallic ACFs substrate, satisfactory removal performance was achieved. The removal efficiency of the metallic ACFs substrate was mainly determined by the properties of the material for adsorption and trapping of organics, and catalytic effects.