Synthetic α-tocopherol has eight isomeric configurations including four 2R (RSS, RRS, RSR, RRR) and four 2S (SRR, SSR, SRS, SSS). Only the RRR stereoisomer is naturally synthesised by plants. A ratio of 1·36:1 in biopotency of RRR-α-tocopheryl acetate to all-rac-α-tocopheryl acetate is generally accepted; however, studies indicate that neither biopotency of α-tocopherol stereoisomers nor bioavailability between them is constant, but depend on dose, time, animal species and organs. A total of forty growing young male mink were, after weaning, assigned one of the following treatments for 90 d: no α-tocopherol in diet (ALFA_0), 40 mg/kg RRR-α-tocopheryl acetate (NAT_40), 40 mg/kg all-rac-α-tocopheryl acetate (SYN_40) and 80 mg/kg feed all-rac-α-tocopheryl acetate (SYN_80). Mink were euthanised in CO2 and blood was collected by heart puncture. Mink were pelted and liver, heart, lungs, brain and abdominal fat were collected for α-tocopherol stereoisomer analysis. The proportion of RRR-α-tocopherol decreased in all organs and plasma with increasing amount of synthetic α-tocopherol stereoisomers in the diet (P≤0·05), whereas the proportion of all synthetic α-tocopherol stereoisomers increased with increasing amount of synthetic α-tocopherol stereoisomers in the diet (P≤0·05). The proportion of α-tocopherol stereoisomers in plasma, brain, heart, lungs and abdominal fat showed the following order: RRR>RRS, RSR, RSS>Σ2S, regardless of α-tocopherol supplement. The liver had the highest proportion of Σ2S stereoisomers, and lowest proportion of RRR-α-tocopherol. In conclusion, distribution of α-tocopherol stereoisomers differs with dose and form of α-tocopherol supplementation. The results did also reveal the liver’s role as the major organ for accumulation of Σ2S α-tocopherol stereoisomers.