In this study, the performance of the electrochemical peroxidation (ECP) process for removing the volatile suspended solids (VSS) content of waste-activated sludge was evaluated. The Fe2+ ions required by the process were obtained directly from iron electrodes in the system. The performance of the ECP process was investigated in various operational conditions employing a laboratory-scale pilot setup and optimized by response surface methodology (RSM). According to the results, the ECP process showed its best performance when the pH value, current density, H2O2 concentration and the retention time were 3, 3.2 mA/cm2, 1,535 mg/L and 240 min, respectively. In these conditions, the introduced Fe2+ concentration was approximately 500 (mg/L) and the VSS removal efficiency about 74%. Moreover, the results of the microbial characteristics of the raw and the stabilized sludge demonstrated that the ECP process is able to remove close to 99.9% of the coliforms in the raw sludge during the stabilization process. The energy consumption evaluation showed that the required energy of the ECP reactor (about 1.8–2.5 kWh (kg VSS removed)−1) is considerably lower than for aerobic digestion, the conventional waste-activated sludge stabilization method (about 2–3 kWh (kg VSS removed)−1). The RSM optimization process showed that the best operational conditions of the ECP process comply with the experimental results, and the actual and the predicted results are in good conformity with each other. This feature makes it possible to predict the introduced Fe2+ concentrations into the system and the VSS removal efficiency of the process precisely.