Flavothione and a number of synthesized hydroxy- (mono- and di-) substituted flavothiones have been thoroughly examined, particularly regarding their absorption, emission, photophysical (triplet yields and lifetimes), and oxygen-photosensitizing characteristics. These were all studied as a function of the nature of the solvent (four), which was particularly critical in terms of aiding in determining the energy and configurational nature of the lowest triplet state as well as the mechanism of intersystem crossing. Theoretical calculations were also performed. Both the location and number of hydroxyl groups have a substantial impact on the nature of the lowest excited triplet state as well as on the relative location of the two lowest excited singlet and triplet states. These in turn affect the magnitude and even the existence of triplet-state occupation as well as the ability to sensitize oxygen (to singlet oxygen). Three groups of compounds exist as characterized by the configurational nature of the triplet and the mechanism of intersystem crossing, or the essential absence of intersystem crossing altogether. The quantum yield of singlet oxygen formation is high for one group where the T(pi, pi*) state is lowest and generally high in another group where the T(n, pi*) state is lowest, except in ethanol where competitive H-atom abstraction occurs. The potential of all hydroxy compounds as photosensitizers is evaluated.