In summary, we have discovered a novel photocatalytic system using two photons of visible light to access high oxidative powers of ≫ +3 V vs. SCE. The key intermediate in the photocatalytic reaction is the excited radical cation, which shows a ps deactivation and, thus, requires the omnipresence of the substrate to avoid slow diffusive encounters for the rare event of bimolecular electron transfer between a substrate and such a short-lived excited state. Once the electron is abstracted from the substrate such as arenes, further downstream coupling events are initiated. The photostable catalysts of type A and B can be easily modified to tune their electronic and, thus, spectral properties for further improvements on the efficiency of the coupling reaction. The system provides a green alternative to existing methods, based on stoichiometric or substoichiometric amounts of toxic and unstable DDQ.