The direct synthesis of stannyl epoxy alcohols 3 from vinylstannanes 1 is described. The procedure involves the photooxygenation of Vinylstannanes 1, which proceeds in a highly regioselective manner with predominant hydrogen abstraction geminal to the stannyl group. Subsequent reaction of the resulting hydroperoxides 2 with Ti(OiPr)4 afforded in a one‐pot procedure the epoxy alcohols 3 in high diastereomeric excess, which ranged from 81:19 to greater than 95:5. This convenient and effective method was applied to acyclic and cyclic vinylstannanes as well as to γ‐trydroxyvinylstannane 1e, which was converted into the stannyl epoxy diol 3e. In this novel hydroxy epoxidation of vinylstannanes the regioselectivity of the singlet oxygen ene reaction (Schenck reaction) is controlled by the stannyl group.