Over the past few years, quantitative determination of alpha- and gamma-CEHC, main urinary metabolites of vitamin E, has been becoming more and more important as a key parameter in assessing oxidative stress and supplementation of tocopherols. The use of deuterated analogues of these metabolites allows their accurate determination even in complex matrixes. While preparation of gamma-CEHC-d(2) has already been described, here we report the first synthesis of alpha-CEHC-d(3) together with alpha-tocopheronolactone-d(3), its oxidation product.