The aim of this study was to determine the concentrations of 24 perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the South Han River and to assess human health risks of exposure to PFAS through ingestion of water in the same river. Surface water samples were collected in March, June, September, and December, 2023 at seven sampling sites in the river. Ten of the 24 PFAS (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFMPA, PFMBA, PFBS, PFOS, and GenX) were detected and PFBA, PFBS, and PFPeA were predominant. The highest concentration level of PFAS in the river was found at the S1 site, and its total concentration ranged from 691 to 1,021 ng/L. The hazard quotient values of four PFAS (i.e., PFBA, PFBS, PFHxA, and GenX) did not exceed one-tenth of the World Health Organization’s acceptable hazard level.