Oxoglaucine (OG) is an oxoaporphine alkaloid, which has been linked to plant defense mechanisms. It contains a phenalenone (PN)–like chromophore, which suggests a role as singlet oxygen (1O2) photosensitizer. Indeed, OG is able to photosensitize 1O2 with 100% efficiency in nonpolar environments, similar to PN. However, this efficiency decreases in polar and protic media, although 1O2 is formed in all environments ranging from benzene to water. OG is a rather inefficient 1O2 quencher (kq= 8 × 105M−1 s−1) unlike the related alkaloids boldine and glaucine, for which an antioxidant role has been suggested. The results of this study contribute to the view that plant defense mediated by PN‐like secondary metabolites may have a photochemical component.