Abstract: Electro-Fenton Technology is an effective process for the treatment of refractory contaminants in wastewater. Howerver, the technolgy has the defect of inconvenient transportation for H₂O₂. In this study, by selecting triethyl phosphate esters (TEP) as the target pollutant and calcium peroxide (CP) as the oxidant, with iron plate as the corrosion anode and iron source, a CP-based electro-Fenton-like system (electro-Fe-CP system) was firstly constructed to investigate its mineralization efficiency of TEP and its affecting factors. The mechanisms of TEP mineralization in the electro-Fe-CP system were then explored via the release trials of H₂O₂ by CP and the quenching experiments. At last, the precipitates formed from the reaction product at different pH values were characterized by scanning electron microscope (SEM), energy-dispersive spectrometry (EDS), X-ray diffractometer (XRD) and Fourier transform infrared (FTIR) spectra. The results showed that when initial pH, the concentration of TEP, the concentration of CP, the size of Fe plate and the current density were 2.5, 20 mg/L, 4 mmol/L, 20 mm×40 mm×1 mm, and 2.50 A/m², respectively, the electro-Fe-CP system achieved a mineralization rate of 94.6% within 20 min. In addition, inorganic anions (Cl⁻, \mathrmNO_3^- , \mathrmHCO_3^- ) had a minor influence on the mineralization of TEP. Quenching experiments indicated that hydroxyl radicals (•OH) were the major active species in the electro-Fe-CP system. Furthermore, the pH significantly affected the composition of the precipitate formed from the reaction products. Specifically, the precipitate at pH 8.5 mainly consisted of iron hydroxide, calcium sulfate, and calcium phosphate, while it might also contain a small amount of hydroxyapatite at pH 10.5. This study confirms the feasibility of utilizing electro-Fenton-like system based on calcium peroxide for treating TEP in water. The possible application scenarios and suggestions for the electro-Fe-CP system were also proposed.