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Penicillin is the most widely used and longest-lived antibiotic in the pharmaceutical industry. It belongs to the bio-fermentation chass of drugs, with a large amount of fermentation exhaust containing volatile organic compounds (VOCs) generated during the process of penicillin production, which have a serious impact on the environment. In this study, the pollution characteristics of the fermented exhaust are studied by using investigation and testing the souces of the pollution and via a health risk assessment model. The main results show that 23 kinds of VOCs were detected in the penicillin fermentation exhaust. The main pollutants included vinyl acetate trifluorotrichloroethane, dichlorotetrafluoroethane, and methylene chloride. In the heating stage, holding stage, cooling stage, and fermentation stage, the proportion of chlorinated hydrocarbons was the highest, followed by esters, and the total amount of these two kinds of substances accounted for more than 90% of total volatile organic compounds (TVOCs). Using the model of health risk assessment, the noncarcinogenic risk value of the total fermented exhaust was 4.98×10