The structure of a new carotenoid, isolated from the fruits of the red tomato-shaped paprika Capsicum annuum L., was elucidated to be (3S,5R,6S,5'R)-3,6-epoxy-5,6-dihydro-5-hydroxy-beta,kappa-carotene-3',6'-dione by spectroscopic analyses, including fast atom bombardment collision-induced dissociation-mass spectrometry/mass spectrometry (FAB CID-MS/MS) and was designated capsanthone 3,6-epoxide. Capsanthone 3,6-epoxide is assumed to be an oxidative metabolite of capsanthin 3,6-epoxide in paprika.