Fluoride ion-mediated anodic methoxylation of 1,1,1-trifluoropropyl-3-(phenylthio)propan-2-ol was successfully carried out to provide the corresponding alpha-methoxylated product, beta,beta,beta-trifluorolactic aldehyde equivalent, which was demonstrated to be a useful CF3-containing building block for diastereoselective carbon-carbon bond formation. The fluoride ion-mediatory system was also successfully applied to anodic intramolecular alkoxylation of 1-(benzylthio)-3,3,3-trifluoro-propan-2-ol and its derivatives to afford the corresponding CF3-containing 1,3-oxathiolanes as a stereoisomeric mixture in good yields. This is the first successful example of anodic intramolecular alkoxylation of saturated organo sulfur compounds. (C) 2018 The Electrochemical Society.