The coal chemical industry produces a large amount of volatile organic compounds (VOCs), and the emission characteristics and associated impact on the environment and health of the residents are still unclear. This study determined the VOC concentrations and compositions in the Jinjie Coal Chemical Industry Park which is located in northern China. The average concentrations of total measured VOCs (TVOCs) in the industrial areas in summer and winter were 231.5 and 103.2 μg/m3, which were higher than those in the residential areas (123.7 and 70.3 μg/m3), respectively. Aromatics, Oxygenated volatile organic compounds (OVOCs), and alkanes were the dominant VOC classes in the industrial areas, while halocarbons, OVOCs, and alkenes had higher compositions in the residential areas where were not only affected by industrial emissions and also other anthropogenic sources. OVOCs contributed over 43% of ozone formation potential (OFP), while aromatics contributed over 61% of secondary organic aerosol (SOA) formation in the Park in both seasons. Using the source apportionment method, biogenic emission and anthropogenic source (gasoline production, coking emission, fuel combustion, solvent coating, and vehicle exhaust) were major contributors to VOCs in residential areas. The industrial-related emissions were the main components of anthropogenic source, accounting for 53.5%–58.7% of the overall VOCs. With reliable estimations of the health aspects, exposures to acrolein (HQ: 7.4–126.6) and formaldehyde (ILCR: 5.5 × 10−3-5.7 × 10−2) posed the highest non-carcinogenic and carcinogenic risks, accounting for 94.3%–98.6% and 55.8%–93.8% of the total HQ and ILCR, respectively. The results demonstrated that substantial environmental and health co-benefits to the residents could be achieved by reducing the industrial emissions from gasoline production, coking process, and diesel-fueled vehicles in the Jinjie Coal Chemical Industry Park. Prioritizing the establishment of efficient air pollution measures and tightening industrial emission standards, especially for hazardous VOCs, are recommended according to the findings of the valuable work.