Abstract— The photolysis of crystal violet oxalate has been studied in aqueous and non‐aqueous solutions and in films of poly(viny1 alcohol) at room temperature. Evidence has been obtained from electron‐spin‐resonance, absorption and fluorescence spectroscopy for the formation of the semireduced dye radical, tri‐(p‐dimethylaminophenyl)methyl, both in solution and in the solid state. Electron spin resonance and luminescence spectra of the radical produced by electrolytic reduction of the dye are also reported.