Polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) are recognized environmental endocrine disruptors, which are environmentally persistent and may bio-accumulate in human bodies. Pregnant and nursing women may pass these pollutants to their babies both trans-placentally and lactationally. We measured and examined correlations of the levels of PCDD/Fs and PCBs in perinatal venous serum, placenta, umbilical-cord serum (representing prenatal exposure), and breast milk (postnatal exposure). Subjects included pregnant women without clinical complication between the ages of 25 and 35, who delivered their babies during 2000.12.01 and 2001.11.30 in central Taiwan. A total of 20 participants were randomly selected from those provided the four biological specimens for analysis of 17 PCDD/Fs, and 12 dioxin-like PCBs and six indicator PCBs using high-resolution gas chromatography/high-resolution mass spectrometry. Higher PCDD/F levels were found in placenta (10.3 TEq-pg/g lipid) and venous serum (9.1 TEq-pg/g lipid) compared to those in breast milk (7.6 TEq-pg/g lipid). Pearson and Spearman correlation analyses showed well association of PCDD/F and PCB levels between different specimens. The total dioxin/PCB level in milk, venous and cord serum can be well predicted by that in placenta through regression functions. This first study of multi-specimen correlation further established rather consistent ratios of these chemical concentrations in various specimens relative to those in venous serum.