A practical stereoselective synthesis is reported for an α-trifluoromethyl-α-alkyl epoxide (1), which is an important pharmaceutical intermediate. The key step involves a chiral auxiliary- controlled asymmetric trifluoromethylation reaction for the introduction of the unique trifluoromethyl-substituted tertiary alcohol stereogenic center in the target molecule. The fluoride-initiated CF3 addition to chiral keto ester 6a proceeded with a diastereoselectivity ...