Pharmaceuticals and personal care products (PPCPs) have been recognized as emerging contaminants in freshwater. In recent years, a lot of monitoring studies have been carried out, and wastewater treatment plants (WWTPs) were identified as a major source of PPCPs. As Ulsan is a metropolitan city and there are more than four rivers and six WWTPs, we conducted the first PPCP monitoring study to investigate the level, pattern, and geographical distribution of PPCPs in Ulsan. We collected 19 river water samples and analyzed 29 PPCPs using an LC/MS/MS. Among the target compounds, 26 compounds were detected from the samples; Antibiotics, analgesic and antipyretics, and beta-blockers were dominant compounds. As lincomycin and atenolol were frequently detected with the highest concentrations, they were listed as priority PPCPs in Ulsan. The highest total concentration of PPCPs was measured at a sampling site near the Eonyang WWTP, demonstrating that the WWTP is an important source of PPCPs. However, the overall spatial distribution of PPCPs suggests that non-point sources are also important in Ulsan.