Abstract: TiO₂ photocatalytic oxidation was used to perform the advanced treatment of discharge wastewater from a coking wastewater treatment station. The effects of reaction time, TiO₂ dosage and initial pH on TOC removal rate of wastewater were tested. The GC/MS technique was used to give a qualitative analysis of wastewater before and after treatment. Thedegradation regularity of wastewater during the TiO₂ photocatalytic oxidationprocess was analyzed. The result showed that under the conditions of reaction time 3 h, TiO₂ concentration 4 g/L and unadjusted wastewater pH, the TOC removal rate of the wastewater was 53.40%. Additionally, the number of species of organic matter was reduced from 66 to 23 in the wastewater after being treated by TiO₂ photocatalytic oxidation. TiO₂ photocatalytic oxidation had better removal efficiency for organic pollutants with the exception of PAHs. During the process of TiO₂ photocatalytic oxidation, the degradation rates of different organic pollutants were as follows: petroleum hydrocarbon > alcohol, acid, aldehyde and other organic pollutants > phenols > benzene derivatives > nitrogen heterocyclic compounds > PAHs.