Photochemical pathways leading to the phototoxicity of the aloe vera constituent aloe emodin were studied. The results indicate a photochemical mechanism involving singlet oxygen to be the most likely pathway responsible for the observed phototoxicity. Aloe emodin was found to efficiently generate singlet oxygen when irradiated with UV light (Φ_Δ = 0.56 in acetonitrile). The survival of human skin fibroblast cells in the presence of aloe emodin was found to decrease upon irradiation with UV light. A further decrease in cell survival was observed in D₂O compared with H₂O, suggesting the involvement of singlet oxygen as the primary pathway. Laser flash photolysis experiments were also carried out on aloe emodin alone and in the presence of various biological substrates. Aloe emodin proved to be relatively photostable (Φ = 1 × 10⁻⁴) and a poor photo-oxidant (E^*_red = 1.02 V). Only absorption bands caused by the triplet state of aloe emodin (λ_max = 480 nm) and the aloe emodin conjugate base (λ_max = 520 nm) were observed in the transient spectra.