The coal gasification (CG) process, while beneficial for producing syngas, poses environmental risks due to the production of highly toxic wastewater containing high concentrations of polycyclic aromatic hydrocarbons (PAHs), phenolics, and cyanides. This study examines the oxidation of pollutants in wastewater from a simulated underground coal gasification (UCG) process, with initial pollutant levels of pH 1.8, total cyanides 21.00 mg/L, total phenols 61.95 mg/L, heavy metals 7.68 mg/L, PAHs 2459 μg/L, and dissolved organic carbon (DOC) 148.0 mg/L. Three oxidation systems (Ce(SO4)2·4H2O, Ce(SO4)2·4H2O + H2O2, and Fenton process with FeSO4 + H2O2) were used to remove pollutants from wastewater from the coal gasification process. In the first system, the oxidising agent was Ce4+ ions, while in the second and third systems, where hydrogen peroxide was added, the oxidising agents were hydroxyl radicals. Using central composite design and response surface methodology (CCD/RSM), the most favourable oxidation conditions were identified for Ce(SO4)2·4H2O (35 min, Ce4+:C molar ratio of 5:1, pH 2.5, temp. 40 °C). For the Ce(SO4)2·4H2O + H2O2 system DOC:Ce4+:H2O2 molar ratio of 1:2:10. Results showed significant reduction in pollutants: Ce(SO4)2·4H2O reduced PAHs, phenols, cyanides, DOC, and heavy metals by 99.40 %, 99.97 %, 97.67 %, 65.34 %, and 90.01 %, respectively; Ce(SO4)2·4H2O + H2O2 achieved reductions of 99.91 %, 99.66 %, 98.14 %, 76.35 %, and 81.45 %; and the Fenton process achieved reductions of 99.91 %, 99.95 %, 95.07 %, 56.49 %, and 89.33 %. An application of alternative oxidation processes (Ce(SO4)2·4H2O and Ce(SO4)2·4H2O + H2O2) is a viable option in removing toxic pollutants with simultaneously cerium recovery.