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Reducing anthropogenic volatile organic compounds (VOCs) is the most effective way to mitigate O3 pollution, which has increased over the past decades in China. From 2012 to 2017, special stainless-steel cylinders were used to collect ambient air samples from the urban area of Beibei district, Chongqing. Three-step pre-concentration gas chromatography–mass spectrometry was used to detect the collected air samples. The composition, concentration, photochemical reactivity, and sources of VOCs in Beibei were analyzed. During the observation period, the annual average VOC concentration was 31.3 ppbv, which was at an intermediate range compared to other cities in China. Alkanes (36.8%) and aromatics (35.6%) were the most abundant VOC groups, followed by halo-hydrocarbons (14.4%) and alkenes (12.6%). The overall trend of seasonal distribution of VOC concentration was high in summer and autumn, and low in winter and spring, with a statistically significant difference between summer and winter concentrations. The ozone formation potential (OFP) showed that alkenes were the most active species, followed by aromatics and alkanes, and summer was the season with the highest OFP (131.6 ppbv). Three major emission sources were identified through principal component analysis (PCA), i.e., vehicle exhaust emissions (66.2%), fuel oil evaporation (24.8%), and industrial sources (9.0%). To ameliorate the air quality within the study area, concerted efforts should be directed towards curtailing traffic emissions and mitigating the release of alkenes, particularly emphasizing more stringent interventions during the summer season. [ABSTRACT FROM AUTHOR]