A pilot study was conducted to provide preliminary data on the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorooctanesulfonamide (PFOSA) in the blood of Canadians. A set of 56 human serum samples was collected from non-occupationally exposed Canadians and analyzed by microbore HPLC-negative ion electrospray tandem mass spectrometry. PFOS was the main component of perfluorinated organic compounds (PFCs) and was detected in all 56 blood specimens at an average concentration of 28.8 ng mL(-1) and a range from 3.7 to 65.1 ng mL(-1). The concentration of PFOA was an order of magnitude lower than that of PFOS and was found only in 16 samples (29%) at concentrations above the limit of quantification (LOQ). PFOSA was not detected at levels above the method detection limit (MDL) in any of the samples. The levels of PFCs observed in the sample group of non-occupationally exposed humans in Canada were similar to the levels reported in a previous US study with a similar sample pool size. Two distinct PFOS isomers in human serum were identified by accurate mass determination.