This paper describes an efficient, sustainable, one-step procedure for synthesizing substituted phenazines and phenoxazinones from commercially available ortho-substituted aromatic amines with very good yield (≥80%) in water. The procedure uses eosin Y (EY) as a photoredox catalyst at room temperature (RT). The highly reactive o-quinone-diimine or o-quinone-imine intermediate was characterized by the HR-MS technique. © 2021 American Chemical Society.