Photolysis of 2-(pentamethyldisilanyloxy)phenylpentamethyldisilane 1 in methanol provides five photoproducts 3, 4, 5, 6, and 7. Compounds 3 and 4 were probably formed from the methanol addition reactions of silene intermediate 2 and the formation of 5, 6, and 7 can best be explained by the nucleophilic attack of methanol to silicon atom in pentamethyldisilanyloxy or pentamethyldisilanyl group of the photoexcited state of 1. Irradiation of 1 in n-hexane gives a photoproduct 6 via silyl radical intermediate 8 and a novel intramolecular cyclization photoproduct 11 via silene 9 and silyl radical intermediate 10. Irradiation of 1 in deaerated methylene chloride in the presence of acetone affords a novel photoproduct 11 and phenol 7 but the expected photoproducts from the reaction of the silene intermediate with acetone were not obtained.