Acrylonitrile is a highly toxic and hazardous pollutant present in industrial wastewater at high concentrations, posing significant environmental and health risks. There is an urgent need for efficient, cost-effective, and environmentally friendly treatment methods for acrylonitrile. The electron-withdrawing –CN group in acrylonitrile offers potential pathways for degradation via superoxide radicals (O2•-), but this approach remains underexplored with limited research efforts. To investigate the degradation mechanism of acrylonitrile by O2•-, we synthesized particle electrodes Fe-Cu@CB using a novel one-step co-hydrolysis method and applied them for the 3D electrochemical degradation of acrylonitrile. Batch experiments showed that acrylonitrile with an initial concentration of 100 mg·L−1 was removed by 95 % at a voltage of 2.73 V (vs. RHE) for one hour. Compared with 2D electrochemical degradation, 3D electrochemical degradation of acrylonitrile increased the removal rate from 57 % to 95 %, and the TOC removal rate was also enhanced from 23.59 % to 88.33 %. Additionally, the energy consumed by this system was remarkably lower than the reported 3D electronic reaction system. Based on electron paramagnetic resonance (EPR), oxygen species (ROS) quenching experiments, and GC–MS results, we proposed a new hydrogenation-oxidation synergistic pathway for acrylonitrile removal, which could be depicted as that acrylonitrile suffered hydrogenation, followed by O2•- reduction, and finally the intermediate products were degraded speedily. Other pollutants in acrylonitrile wastewater such as acrylic acid, acrylamide, and fumaronitrile could also be eliminated in this reaction system, and the degradation efficiency varied with the electronic structure of the pollutants. These findings offer new insights into the treatment of acrylonitrile wastewater and present a highly efficient, sustainable solution for industrial pollutant degradation.