A new minor carotenoid, β-citraurin epoxide (3-hydroxy-5,6-epoxy-5,6-dihydro-8'-apo-β-caroten-8'-al) and several isomers of violaxanthin (5,6,5',6'-diepoxy-5,6,5',6'-tetrahydro-β,β-caroten-3,3'-diol) have been identified in Valencia orange peel. The previously reported occurrence of apo-10'-violaxanthal (3-hydroxy-5,6-epoxy-5,6-dihydro-10'-apo-β-caroten-10'-al) and apo-12'-violaxanthal (3-hydroxy-5,6-epoxy-5,6-dihydro-12'-apo-β-caroten-12'-al) has been confirmed, and their syntheses are described. The quantitative determination of the carotenoids has also been performed.