Abstract Perfluoroalkyl substances (PFASs) are ubiquitous in the environment world-wide. Our overall objective was to assess the exposure to PFASs experienced by delivering women and their new-borns in the industrial city of Norilsk (arctic Russia) and the rural Aral Sea region of Uzbekistan, with the secondary objective of evaluating the distribution of PFASs between blood cell and plasma fractions. Six PFASs were detected in every sample from Norilsk city with the plasma concentration sequence of: PFOS≫PFOA>PFNA>FOSA>PFHxS>PFUnDA. In the Uzbekistani samples, only PFOS was reported above the MDL (0.08ng/mL). The median plasma concentrations of PFOS of 11.0ng/mL for the Norilsk mothers was comparable to that reported for western countries, while that for Uzbekistan was considerably lower (0.23ng/mL). Apparent increases in the maternal-cord concentration ratios for both whole blood and plasma were evident with the length of the carbon chain for both the carboxylate and the sulfonate PFASs. The median value of this ratio for FOSA in plasma was the lowest, while that for whole blood was the highest. Other than for FOSA, the observed plasma–whole blood concentration ratios for maternal and umbilical cord blood were consistent with a priori calculations using appropriate packed cell and plasma volumes for neonates and pregnant women at term. Clearly FOSA favored whole blood, and acid–base equilibrium calculations suggested that the resonance-stabilized sulfonamidate ion resides in the blood cell fraction. Thus for PFASs and related compounds with pKa values with magnitudes comparable to physiological pH, it is pertinent to measure the cell-associated fraction (separately or as whole blood). Our study illustrates that consideration of both the physico-chemical properties of the contaminants and the physiological attributes of blood matrices were helpful in the interpretation of our findings.