Tocopherol sources in diets are often a combination of all-rac-α-tocopheryl acetate (synthetic α-tocopherol) from vitamin supplements and natural tocopherols and 2R-(4′R, 8′R)-5,7,8-trimethyltocotrienol (α-tocotrienols) from the feed sources. Synthetic α-tocopherol consists of 8 different stereoisomers including 2R-(4′R, 8′R)-5,7,8-trimethyltocol (RRR-α-tocopherol), 2R-(4′S, 8′R)-5,7,8-trimethyltocol (RSR-α-tocopherol), 2R-(4′R, 8′S)-5,7,8-trimethyltocol (RRS-α-tocopherol), 2R-(4′S, 8′S)-5,7,8-trimethyltocol (RSS-α-tocopherol), 2S-(4′S, 8′S)-5,7,8-trimethyltocol (SSS-α-tocopherol), 2S-(4′R, 8′S)-5,7,8-trimethyltocol (SRS-α-tocopherol), 2S-(4′S, 8′R)-5,7,8-trimethyltocol (SSR-α-tocopherol), and 2S-(4′R, 8′R)-5,7,8-trimethyltocol (SRR-α-tocopherol). The pre-absorption metabolism of tocopherols and tocotrienols in ruminants differs from monogastric animals due to the extensive microbial fermentation in the anaerobic rumen. The current study investigated the impact of toasting and decortication of oats on metabolism in the digestive tract (synthesis, digestion), and intestinal digestibility of tocopherols in dairy cows by using 4 ruminal and intestinal cannulated Danish Holstein cows in a 4 × 4 Latin square design for 4 periods. Cows were fed a total mixed ration ad libitum containing different forms of oats: whole oat, decorticated oat, toasted oat, and decorticated toasted oat, all rolled before mixed ration. Overall means across 4 treatments were statistically analyzed, testing whether overall means were different from zero. Decortication or toasting did not affect the balance or digestibility of α-tocopherols in rumen. Average across treatments showed the ruminal degradation of synthetic α-tocopherol (279 mg/d, P = 0.02; P-value shows that average across treatments is different from zero), synthetic 2R-α-tocopherol (133 mg/d, P < 0.01; summation of RRS-, RSR- and RSS-α-tocopherol), and 2S-α-tocopherol (190 mg/d; P < 0.01, summation of SSS-, SRS-, SSR, and SRR-α-tocopherol), while RRR-α-tocopherol was formed in the rumen (221 mg/d, P = 0.10). The average across treatments showed that small intestinal digestibility of tocopherols ranked in the following order: α-tocotrienol > natural α-tocopherol > synthetic atocopherols > 2R-(4'R, 8'R)-,7,8-dimethyltocol (γ-tocopherol). The average across treatments for small intestinal and feed-ileum digestibility ranked in the following order: RRR-a-tocopherol > synthetic 2R-α-tocopherol > 2S-α-tocopherol. Results showed the first evidence for RRR-α-tocopherol formation under anaerobic conditions in the rumen. In addition, synthetic γ-tocopherol stereoisomers, g-tocopherol and a-tocotrienol were degraded in the rumen. There was a discrimination against absorption of synthetic 2R- and 2S-α-tocopherol in the small intestine.