Human serum and plasma from Sweden (n=17), the United Kingdom (the UK) (n=13) and Australia (n=40) were analyzed by high performance liquid chromatography coupled to mass spectrometry. The objective was to identify different perfluorooctane sulfonate (PFOS) isomers. Similar isomer patterns typical for the electrochemical fluorination (ECF) process were found for all samples. The linear PFOS (L-PFOS) was the major isomer found (58-70%) followed by the monosubstituted PFOS isomers 1/6-CF(3)-PFOS (18-22%) and 3/4/5-CF(3)-PFOS (13-18%). Disubstituted isomers were also detected. The percentage of L-PFOS found in the serum and plasma samples was lower compared to a standard PFOS product (76-79%). The pattern of PFOS isomers in human serum and plasma may be suggestive concerning potential isomeric discrimination since PFOS is only produced by ECF. Possibilities for such isomer discrimination are discussed. Significant higher content of L-PFOS (68%) in Swedish samples compared to Australia and the UK (59%) was also found, which may suggest differences in exposure sources for humans.