A detailed study on the radical of rhodamine 6G, a key intermediate in photoredox catalysis, is presented. Various methods of its preparation (photoinduced electron transfer, electrochemistry), its spectroscopic characterization, stability, oxidation, photoionization and transient spectroscopic study have been investigated. Photooxidation of reduced rhodamine 6G has been established as a sensitive method for determination of dissolved oxygen. Photoionization of rhodamine 6G radical was found to be strongly solvent-dependent and the released electrons were detected as photoinduced current in a spectroelectrochemical OTTLE cell. This process was identified as an extreme case of consecutive photoinduced electron transfer (conPET) mechanism. The electrofluorochromism of rhodamine 6G radical has been studied by a novel apparatus suitable for simultaneous analysis of electrochemical, absorption and emission properties.[a] Dr.