A total of 100 serum samples from 50 new couples (none of the females in this study has ever been pregnant) in Tianjin, North China, were analyzed for eleven perfluoroalkyl acids (PFAAs) with isomer-specific method. Among all samples, total perfluorooctanesulfonate (∑PFOS, mean 11.3 ng/mL) was predominant followed by total perfluorooctanoate (∑PFOA, 2.95 ng/mL), perfluorodecanoate (PFDA, 1.17 ng/mL), perfluorononanoate (PFNA, 0.93 ng/mL) and perfluorohexanesulfonate (PFHxS, 0.67 ng/mL). The mean concentrations of ∑PFOS and PFHxS in males (14.2 and 0.89 ng/mL) were significantly higher (p=0.001) than in females (8.36 and 0.45 ng/mL). No statistical difference between genders was observed for the other PFAAs. This suggests that menstruation is one important elimination pathway for ∑PFOS and PFHxS in females. Linear PFOA was the dominant isomer with mean proportion of 99.7%, suggesting that telomeric PFOA (and its precursors), which contains almost pure linear isomer, might be the dominant exposure source of PFOA in Tianjin. On average, the proportion of linear PFOS (n-PFOS) was 59.2% of ∑PFOS, which was lower than that in technical PFOS products (ca. 70% linear). Except perfluoroisopropyl PFOS, all the other monomethyl branched PFOS isomers were enriched in human serum compared to the commercial products, suggesting the monomethyl branched PFOS precursors were preferentially biotransformed in humans.