The reaction pathways following electronic excitation of 10-methyl phenothiazine (MPS) in the presence of oxygen have been investigated as a contribution to establish the mechanisms involved in the phototoxic reactions related to phenothiazine drugs. In the context of previously published results, the pathways of oxidation via the radical cation and/or by reactive oxygen species, such as singlet oxygen and superoxide anion, are of particular interest. The effects of polarity of the medium as well as of proton donors on the different reaction pathways, in particular on the formation of reactive oxygen species and the intermediates of the oxidation of 10-methyl phenothiazine, have been investigated. No reaction was observed in non-polar solvents. In polar solvents, both self-sensitized and sensitized singlet oxygen generation lead to the oxidation of MPS and the production of 10-methyl phenothiazine sulfoxide (MPSO) most probably via a zwitterionic persulfoxide. During self-sensitized photooxidation of MPS in the presence of proton donors, such as carboxylic acids, the zwitterionic intermediate is protonated to the corresponding cation that in turn facilitates the reaction with a second molecule of MPS. In the presence of strong acids however, the formation of the radical cation of MPS and of the superoxide anion, by electron transfer from the triplet excited state of MPS to molecular oxygen, competes efficiently with singlet oxygen formation. In this case, the scavenging of the superoxide anion by protons to yield its conjugated acid (hydroperoxyl radical) and the subsequent disproportionation of the latter prevents back electron transfer.