The formation and reactivity of excited states and free radicals from primaquine was studied in order to evaluate the primary photochemical reaction mechanisms. The excited primaquine triplet was not detected, but is likely to be formed with a short lifetime (< 50 ns) and with a triplet energy < 250 kJ/mol as the drug is an efficient quencher of the fenbufen triplet and the biphenyl triplet, and forms -is eliminated as a degradation pathway in the photochemical reactions. Impurities in the raw material and photochemical degradation products initiate photosensitized degradation of primaquine in deuterium oxide, prevented by addition of the 1 O 2 quencher sodium azide. Photosensitized degradation by formation of 1 O 2 is thus important for the initial photochemical decomposition of primaquine, which also proceeds by free radical reactions. Formation of PQH 2+