To solve the problem of the poor treatment of high concentration landfill leachate, an electro-assisted ultraviolet (UV)/zero-valent iron (ZVI) synergic activated persulfate (PS) system was used to treat landfill leachate. The effects of PS and ZVI dosage, initial pH value, and current density on the removal efficiency of COD and NH3-N in landfill leachate were investigated. The treatment effects of single PS, single electrochemical, UV/PS, electro-assisted ZVI activated PS, and electro-assisted ZVI/UV co-activated PS were compared. At the same time, UV-visible and three-dimensional fluorescence spectroscopy were performed on the landfill leachate before and after treatment. The results show that under the optimal conditions of initial pH = 3, the dosage of PS/12COD = 1, ZVI = 1.5 g/L, current density 62.5 mA/cm2, and t = 6 h, most of the macromolecular organic substances such as humic acid and fulvic acid were removed. Removal efficiencies of COD, NH3-N, and Chroma reached 81.99%, 89.90%, and 99.75%, respectively. The BOD5/COD value increased from 0.23 to 0.46. In addition, the radical identification results showed that the degradation of COD was due to the combined action of sulfate radicals (SO4•−) and hydroxyl radicals (•OH) and that SO4•− was dominant. The combined means of synergistic activation of PS for landfill leachate treatment was significantly better than that of single means of PS activation, confirming that electrically assisted ZVI/UV synergistic activation of PS is a promising method for landfill leachate treatment.