Phthalates (PAEs) are frequently detected in the water environment and pose a severe threat to the ecosystem and human health. Electro-Fenton technology is regarded as an effective approach to degrade PAEs; however, the preparation of inexpensive and efficient cathode materials has restricted its further application. In this study, Fe/Co bimetallic sites were incorporated into solid waste wine lees to synthesize highly active heterogeneous catalyst, and dimethyl phthalate (DMP) was chosen as the target pollutant to investigate the activity of the catalyst. Both the degradation of DMP and the removal of total organic carbon (TOC), the performance of Fe/Co co-modified biochar (FeCo@NOPC) is superior to that of Fe (Co) alone (Fe@NOPC/Co@NOPC) and modified biochar (NOPC). Under neutral conditions. Within 5 h, the DMP removal rate reached 89 % and TOC was reduced by approximately 40 %. The mechanism study reveals that the degradation of DMP is mainly attributed to the OH generated by the cathode, and the anodic oxidation and cathode adsorption only play minor roles. Finally, the degradation path of DMP was analyzed by LC-MS technique. This study offers a novel way to utilize solid waste and reduce the cost of heterogeneous electro-Fenton system.