Acrylonitrile was recently proposed to be designated as a high-priority substance for risk evaluation by the U.S. Environmental Protection Agency (EPA) under the Toxic Substances Control Act (TSCA). Past research has characterized the health effects of acrylonitrile and the worker population's exposure to it. However, there has been limited assessment of the general population's exposure to acrylonitrile. The objective of this study was to characterize general population exposure to acrylonitrile via the ambient air and to assess the suitability of EPA monitoring and modeled data for use in regulatory risk assessment. Overall, key findings from this study suggest that general population exposure to acrylonitrile from the ambient air is low and EPA's Air Quality System (AQS) data is well suited for general population exposure evaluations. These results benefit the general public in understanding their potential exposure to acrylonitrile, the EPA in informing their TSCA risk evaluation for acrylonitrile, and other researchers aiming to utilize AQS for general population exposure assessments.