This present paper was focused on the manufacture of activated carbon (AC) and its application in the electrokinetic remediation (EKR) technology on removal of the heavy metals (HMs) from the municipal solid waste incineration fly ash. AC was produced from Neosinocalamus affinis (NF) by chemical activation with H3PO4 in N2 atmosphere, the effects of activation temperatures, soaking time and impregnation ratios on the adsorption capacity of AC on HMs were examined through equilibrium adsorption experiments. The AC produced under the condition of 450 °C of activation temperature, 10 h of soaking time and 1.5 of impregnation ration was applied in the EKR experiment. The addition of AC in the S3-region of the electrolyzer could effectively improve the removal efficiencies of HMs. The technical parameters of voltage gradient, processing time and proportion were further optimized in the coupled experiments, the maximum removal of Cu, Zn, Cd, and Pb was 84.93%, 69.61%, 79.57%, and 78.55% respectively obtained under the optimal operating conditions of 2 V/cm of voltage gradient, 8 d of processing time and 20% of proportion.