The chiral allylic alcohols 1a-d and their acetate (1e) and silyl ether (1f) derivatives have been oxidized by the H2O2/MoO42- system, a convenient and efficient chemical source of singlet oxygen. This chemical peroxidation (formation of the allylic hydroperoxides 2) has been conducted in various media, which include aqueous solutions, organic solvents, and microemulsions. The reactivity, chemoselectivity, and diastereoselectivity of this chemical oxidation are compared to those of the sensitized photooxygenation, with the emphasis on preparative applications in microemulsion media. While a similar threo diastereoselectivity is observed for both modes of peroxidation, the chemoselectivity differs significantly, since in the chemical oxidation with the H2O2/MoO42- system the undesirable epoxidation by the intermediary peroxomolybdate competes efficiently with the desirable peroxidation by the in situ generated singlet oxygen. A proper choice of the type of microemulsion and the reaction conditions furnishes a high chemoselectivity (up to 97%) in favor of threo-diastereoselective (up to 92%) peroxidation.