The actual harmful effects of industrial wastewater can not be reflected by the conventional water quality index. Therefore, the change in dissolved organic matter and the genetic toxicity of petrochemical wastewater were observed in the current study by examining the wastewater treatment plant of a large petrochemical enterprise in Northwest China. Using XAD-8, MSC, and DA-7 resins, the wastewater was separated into six fractions, namely, hydrophobic acid (HOA), hydrophobic neutral (HOB), hydrophobic alkaline, hydrophilic acid, hydrophilic alkaline, and hydrophilic neutral. Umu-test was used to detect the genetic toxicity of the wastewater samples, and fluorescence spectra were also obtained to examine genetic toxic substances. The results show that wastewater treatment facilities can effectively reduce the concentration of organic matter in petrochemical wastewater ( <0.05). However, the mixing of aniline wastewater can increase the amount of organic carbon ( <0.05) and can overload facilities. This finding shows that the mixed collection and joint treatment of different types of petrochemical wastewater can affect the water quality of the effluent. Particularly, hydrophobic substances can be difficult to remove and account for a relatively large proportion of the effluent. The mixture of aniline wastewater can increase the genetic toxicity of the effluent ( <0.05), and biologic treatment can not effectively decrease the toxicity. Most of the genetic toxicology may exist in the HOA and HOB fractions. Fluorescence spectroscopy also confirms this result, and tryptophan-like substances may play an important role in genetic toxicity.