The treatment of leachate from most incineration plants in China often involves the use of “membrane bioreactor (MBR) + reverse osmosis” technology. However, this process faces challenges due to the high concentration of fulvic acid in the reverse osmosis system influent, resulting in membrane fouling. In this study, a persulfate synergistic electrochemical system(EC+PS system) was used to reduce the fulvic acid concentration. The study focused on identifying the main active substances responsible for removing fulvic acid in the system. The effect of initial pH value, persulfate dosage(PS), current density, plate space, NaCl concentration on the degradation of fulvic acid was investigated. The results showed that fulvic acid removal mainly relied on Cl- provided by HClO,·OH and SO4-· in succession. The fulvic acid removal rate decreased slightly with increasing initial pH and plate spacing, exhibited an initial increase followed by a decrease with rising initial PS concentration, showed an initial increase followed by stability with increasing current density, and slightly decreased with the increase of Cl- concentration. Both current density and persulfate dosage were identified as the main influencing factors for fulvic acid removal. In practical applications, the leachate effluent from the MBR of an actual incinerator was treated using the EC+PS system under a current density 30 mA/cm², potassium persulfate 9 g/L and reaction time 6 h. Three-dimensional fluorescence spectrum analysis showed that the removal rate of fulvic acid in both visible and ultraviolet regions reached 98.65% and 97.80%, respectively, indicating the effectiveness of the EC+PS system in removing fulvic acid from real wastewater samples.