Electro-peroxone (EP) is a novel technique for the removal of refractory organic contaminants (ROCs), while the role of anode in this system is neglected. In this work, the EP system with graphite felt anode (EP-GF) and activated carbon fiber anode (EP-ACF) was developed to enhance ibuprofen (IBP) removal. The results showed that 91.2% and 98.6% of IBP was removed within 20 min in EP-GF and EP-ACF, respectively. Hydroxy radical (O⋅H) was identified as the dominant reactive species, contributing 80.9% and 54.0% of IBP removal in EP-ACF and EP-GF systems, respectively. The roles of adsorption in EP-ACF and direct electron transfer in EP-GF cannot be ignored. Due to the differences in mechanism, EP-GF and EP-ACF systems were suitable for the removal of O⋅H-resistant ROCs (e.g., oxalic acid and pyruvic acid) and non-O⋅H-resistant ROCs (e.g., IBP and nitrobenzene), respectively. Both systems had excellent stability relying on the introduction of oxygen functional groups on the anode, and their electrolysis energy consumption was significantly lower than that of EP-Pt system. The three degradation pathways of IBP were proposed, and the toxicity of intermediates were evaluated. In general, carbon anodes have a good application prospect in the removal of ROCs in EP systems. Display omitted •GF and ACF anodes exhibited the excellent performance for the IBP removal in EP system.•O⋅H was dominant reactive species, contributing 80.9% to IBP removal in EP-ACF system.•O⋅H and DET separately contributed 54.0% and 33.0% to IBP removal in EP-GF system.•EP-GF system showed the superior stability due to the introduced OGs on GF anode.