A three-component reaction of alkenes, aldehydes, and hydroperoxides catalyzed by FeCl(2) to beta-peroxy ketones has been achieved. This three-component reaction can be also applied to the synthesis of a-carbonyl epoxides, through either a stepwise base-induced epoxidation of the separated beta-peroxy ketone products or a one-pot process by simply adding base to the reaction mixture after the completion of the three-component reaction.