With use of deuterium-labeled isotopes of RRR-and all-rac-α-tocopheryl acetate, the transport of vitamin E in pregnancy was evaluated to determine whether the placenta discriminates between these compounds. Fifteen pregnant subjects were recruited 5 d before delivery to receive 15, 30, 75, 150, or 300 mg vitamin E/d in capsules containing d3-RRR-α-tocopheryl acetate and d6-all-rac-α-tocopheryl acetate (1:1, by wt). Maternal blood was obtained before dosing, at hospital admission, and at parturition. Cord blood samples were obtained at parturition. Deuterium-labeled and unlabeled tocopherol contents were determined by gas chromatography-mass spectrometry in plasma and lipoproteins (chylomicrons, VLDL, LDL, and HDL). Maternal plasma and lipoproteins obtained at delivery had higher concentrations of d3-RRR-α- tocopherol than d6-all-rac-α-tocopherol regardless of the vitamin E dose administered (P < 0.05). Cord plasma at delivery also had higher concentrations of d3-RRR-α-tocopherol than d6-all-rac-α-tocopherol in plasma irrespective of the dose administered (P < 0.05). In lipoproteins isolated from cord blood, tocopherol concentrations were greatest in the HDL fraction (P < 0.05), whereas in maternal blood they were greatest in the LDL fraction (P < 0.05). We conclude that the placental-fetal unit, the fetal liver, or both further discriminate between RRR- and all-rac-α-tocopherol.