Individual polychlorinated biphenyl (CB) congeners in adipose and whole blood tissues of a capacitor manufacture worker (occupational/accidental exposure) and of the general population were determined. Nondestructive sample cleanup and multidimensional gas chromatography-electron capture detection (MDGC-ECD) techniques were applied. Special attention was given to the toxicologically relevant congeners CB-77, CB-126, CB-169, CB-105, CB-114, CB-118, CB-156, CB-167, and CB-189 (IUPAC). Lipid-based tissue contents of sigma CBs were higher in the occupationally/accidentally exposed worker (adipose = 7,000 ng/g; whole blood = 11 ng/g) than in the general population (adipose = 300 ng/g; whole blood = 1.9 ng/g). Among the non-ortho Cl CBs, CB-77 was below detection limit (〈 1.0 pg/g). The contents of CB-126 for the capacitor manufacture worker were 2,000 and 3 pg/g, and in the general population were 100 and 2 pg/g for adipose and whole blood, respectively. The corresponding data for CB-169 were 3,500 and 4 for adipose and whole blood, respectively, in the exposed worker, and 40 and 2 for adipose and whole blood, respectively, in the general population. Congeners with highest contents were CB-153, CB-138, CB-180, CB-170, and CB-187. These congeners possess chlorine substitution patterns, making them resistant to metabolism. X/153 ratios suggest that both PB and 3-MC type cytochrome P-450 enzymes were induced in the exposed worker, as well as in the general population.