Volatile N-Nitrosamines (NAs), including N-nitrosodimethylamine (NDMA), an emerging contaminant in drinking water, have been reported to induce cancer in animal studies. This study aims to investigate the regional and seasonal distributions of the concentrations of NDMA, one of the most commonly found NAs with high carcinogenicity, in municipal tap water in Korea. NDMA in water samples was quantitatively determined using high-performance liquid chromatography-fluorescence detection (HPLC-FLD) as a 5-dimethylamino-1-naphthalenesulfonyl (dansyl) derivative after optimization to dry the SPE adsorbent and remove dimethylamine prior to derivatization. Tap water samples were collected from 41 sites in Korea, each of which was visited once in summer and once in winter. The average (±standard deviation) NDMA concentration among all the sites was 46.6 (±22.7) ng/L, ranging from <0.13 to 80.7 ng/L. Significant NDMA differences in the regions, excluding the Jeju region, were not found, whereas the average NDMA concentration was statistically higher in winter than in summer. A multiple regression analysis for the entire data set indicated a negative relationship between NDMA concentration and water temperature. High levels of NDMA in Korea may pose excessive cancer risks from the consumption of such drinking water.