The electrochemical activation of peroxymonosulfate (PMS) and peroxydisulfate (PDS) for pollutant degradation has gained increasing attention. In this work, reticulated vitreous carbon (RVC) electrodes were prepared at a low cost and investigated for the cathodic activation of PMS/PDS for Acid Orange 7 degradation. The RVC was characterized by SEM, TGA, XRD, Raman spectroscopy, XPS, EIS, and compression test. The superior activity outperformed previous reports in terms of low current density operation (1–10mA/cm2), high degradation rates (0.13–0.49min−1), low energy consumption (0.03–0.23 kWh/m3/order) without involvement of catalysts. The process was optimized for current density, PMS dosage, pollutant concentration, pH, water matrix, and supporting electrolyte. Under the optimal current density (3mA/cm2), the addition of 0.5mM of PMS boosted the degradation rate by 9.6 times to 0.4470min−1 and reduced the electrical energy consumption by 90.1% to 0.0243 kWh/m3/order in 50mM of Na2SO4. Moreover, up to 117mg/L of H2O2 was produced in 1hour by the reduction of oxygen, with current efficiencies between 78–24%. The process showed little deterioration in 10 cycles, worked for a variety of pollutants, and was not affected by the water matrix. The H-cell experiments confirmed that 90% degradation took place on the cathode. Scavenging experiments and electrochemical tests suggested that the transitional state of PMS⁎ and O2•− mediated the direct electron transfer mechanism for AO7 degradation. Eighteen degradation products were identified by HPLC-MS and categorized into 4 degradation pathways. Finally, their toxicity was assessed by the ECOSAR programme.