Acid Orange 7 (AO7), as a most common and widely used synthetic dyes in the printing and dyeing industry, was hardly degradable by traditional wastewater treatment methods. Here, activated carbon fiber (ACF) as an in-situ regenerated cathodic adsorbent in the electrochemical/Fe3+/peroxymonosulfate process (EC/ACF/Fe3+/PMS) was firstly investigated for AO7 removal and compared with several different processes. The results indicated that the effective adsorption of AO7 on ACF can be enhanced under electrolytic conditions, while the adsorbed AO7 on ACF can be completely degraded and mineralized in EC/ACF/Fe3+/PMS process resulting in the in-situ regeneration of ACF. Besides, the electrical energy per order values were investigated, which showed an apparent reduction of electrical energy consumption from 0.42831 to 0.09779 kWh m-3 when ACF-cathode replaced Pt-cathode. Further study revealed that higher conversion rate of Fe2+ from Fe3+ was observed with ACF-cathode. It deserved to be mentioned that the removal efficiency of AO7 was satisfactory and stable even after reusing ACF cathode for 10 times. Furthermore, structure and elements of ACF surface were investigated, which indicated the structure of ACF was intact in EC/ACF/Fe3+/PMS due to inhibition of ACF corrosion by electron migration at cathode. In addition, the total iron content of the effluent in EC/ACF/Fe3+/PMS was lower than that of EC/Fe3+/PMS due to the deposition of iron on ACF-cathode surface. Therefore, advantages of EC/ACF/Fe3+/PMS for AO7 degradation were not only a much higher oxidation efficiency and in-situ regenerated cathodic adsorbent, but also a lower electrical energy consumption and lesser iron ions contents in the effluent.