Leachates, particularly those from mature landfills, are difficult to treat by biological processes because of their high toxicity and low biodegradability. Therefore, the development of new treatment technology is necessary. The treatment of landfill leachate by peroxicoagulation and solar peroxicoagulation using a batch electrolytic reactor with a Fe cathode and a Cu anode is proposed. The tested operational variables included pH (2.8 and 8.2), current density (11 and 16 mA cm−2), treatment time (5, 10, 15, 20, 25, and 30 min), and presence of solar ultraviolet (UV) light and were collected using a compound parabolic collector. The optimum conditions were a pH, current density, and treatment time of 2.8, 16 mA cm−2, and 10 min, respectively. The presence of UV did not have a significant effect. The chemical oxygen demand and biochemical oxygen demand removed were 62.3% and 55.5%, respectively. The results of UV-visible absorption, fluorescence, and Fourier transform infrared spectroscopy measurements confirm the oxidation process.