Chinese chemical companies often cluster in specific regions, leading to concentrated emissions of various chemicals and pollutants, which poses significant risks to ecosystems and human health. Water samples were collected from the rivers near the chemical industrial park (CIP) in Jiangsu Province, China, and utilized suspect screening to identify pollutants. This study aimed to examine the correlation between these pollutants and those detected in the effluent from the companies or wastewater treatment plants (WWTPs) within the CIP, thereby providing a scientific basis for government management decisions. In the rivers surrounding the CIP, over 50 types of pollutants were found, with 26 identified near the river estuary, half of which were pesticides. Analysis indicated that sites closest to the WWTPs discharge outlets exhibited heightened pollutant levels, suggesting the release of challenging-to-treat pollutants into the environment. Additionally, compounds consistent with those used by the companies were detected in rivers without WWTP discharge, underscoring that pollutants originating from CIP enterprises are not solely attributed to wastewater treatment plant discharges. This information underscores the need for comprehensive and effective environmental management and monitoring strategies within chemical industrial parks.