Abstract: The investigation presented in this paper explores the mechanistic aspects and synthetic potentials of PET promoted reductive activation of selenosilane 1a to its radical anion 1a-. PET activation of 1a is achieved through a photosystem comprising a light- absorbing electron-rich aromatic (ERA), such as DMN or DMA, as an electron donor and ascorbic acid as a co-oxidant. The evidence for the ET from excited singlet states of DMN ...