The objective of this study was to evaluate the congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in Korean serum samples as biological markers. Serum samples from 103 participants were analyzed. Participants consisted of 28 workers in municipal solid waste incinerators (MSWIs), and 21 men and 54 women who had lived for at least 3 years prior to 2002 in areas within 300 m of incinerators in large Korean cities. Serum samples were analyzed for 17 PCDD/PCDFs congeners by high resolution gas chromatography-high resolution mass spectrometry. Geometric mean (GM) PCDD/PCDF levels in the serum samples were 3.14, 8.04, 6.12 and 6.60 pg TEQ/g lipid for workers, male residents, female residents and the sum of male and female residents, respectively. The GM PCDD/PCDF level in the serum of workers was not significantly different from the values for residents near MSWIs. In the 75 participants who resided near MSWIs, the congeners that most contributed to the total TEQ were 1,2,3,6,7,8-hexachlorodibenzofuran (1,6-HxCDF), 2,3,4,7,8-pentachlorodibenzofuran (4-PeCDF), 1,2,3,4,6,7,8-heptachlorodibenzofuran (1,4,6-HpCDF), 1,2,3,7,8,9-hexachlorodibenzofuran (1,9-HxCDF), 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (1,4-HxCDD), 1,2,3,6,7,8-hexachlorodibenzo-p-dioxin (1,6-HxCDD). In the workers, the congeners that made the greatest contribution were 1,6-HxCDD, 4-PeCDF, 1,2,3,4,6,7,8-heptachlorodibenzop-dioxin (HpCDD), and 1,6-HxCDF. In conclusion, the serum TEQ levels for PCDD/PCDFs in the incinerator workers and residents near the MSWIs in Korea were lower than those reported for other countries. Comparison of the PCDD/PCDF levels of workers at MSWIs and nearby residents revealed no significant enhancement of PCDD/PCDF exposure in workers. PCDD/PCDF intake from animal origin was assumed to be lower than that of Europeans. Further studies of Korean foods are needed to clarify the exposure route for PCDD/PCDFs in the Korean population.