Irradiation with visible light of a secondary alcohol, benzhydrol, in the presence of molecular oxygen within a titanium-substituted mesoporous molecular sieve, Ti-MCM-41, led to the formation of the alpha-hydroperoxoalcohol and then hydrogen peroxide. The peroxide species reacted in situ with alkenes and sulfides and led to the titanium center catalyzed selective formation of epoxides from alkenes and sulfoxides from sulfides. The cascade of reactions represents a new method for the photoactivation of oxygen in the presence of alcohols.