It is very important to choose a suitable method and catalyst to treat coking wastewater. In this study, Fe-Ce-Al/MMT catalysts with different Fe/Ce molar ratios were prepared, characterized by XRD, SEM, and N 2 adsorption/desorption, and treated with coking wastewater. The results showed that the optimal Fe-Ce-Al/MMT catalyst with a molar ratio of Fe/Ce of 7/3 has larger interlayer spacing, specific surface area, and pore volume. Based on the composition analysis of real coking wastewater and the study of phenol simulated wastewater, the response surface test of the best catalyst for real coking wastewater was carried out, and the results are as follows: initial pH 3.46, H 2 O 2 dosage 19.02 mL/L, Fe 2+ dosage 5475.39 mL/L, reaction temperature 60 °C, and reaction time 248.14 min. Under these conditions, the COD removal rate was 86.23%.