The enhancement effect of Cu/Fe-amination-polyacrylonitrile (Cu/Fe-AO-PAN) as a catalyst for H₂O₂ produced by dielectric barrier discharge plasma (DBDP) on 4-fluorophenol (4-FP) degradation was explored. The addition of Cu/Fe-AO-PAN significantly increased the 4-FP removal rate and degradation energy efficiency from 61.0% and 1777 mg kWh^-1 to 75.6% and 2203 mg kWh^-1, respectively. The homologous total organic carbon (TOC) removal and defluorination efficiency were both increased (from 52.1% to 63.0% and 48.0% to 54.2%, respectively). The role of H₂O₂ production was investigated by influencing parameter analysis and radical scavenging experiments. •OH was verified to be a reactive species that increased 4-FP abatement, and was generated through electron transfer and binuclear metal complex formation between Cu/Fe-AO-PAN and H₂O₂ during the Fenton-like process. This study provides a new insight into efficient wastewater treatment under DBDP process.