This article describes a highly effective catalytic asymmetric epoxidation method for olefins using potassium peroxomonosulfate (Oxone, Dupont) as oxidant and a fructose-derived ketone (1) as catalyst. High enantioselectivies have been obtained for trans-disubstituted and trisubstituted olefins which can bear functional groups such as tributylsilyl ether, acetal, chloride, and ester. The enantiomeric excesses for cis-olefins and terminal olefins are not high yet. The current epoxidation shows that the catalyst efficiency is enhanced dramatically upon raising the pH. Mechanistic studies show that the epoxidation mainly proceeds via a spiro transition state, which provides a model for predicting the stereochemical outcome of the reaction. The planar transition state is likely to be the main competing pathway. The extent of the involvement of the planar mode is subject to the steric effect of the alkyl groups on the olefins.