The photooxygenation of the 1,4‐disubstituted 2,3‐dimethyl‐2‐butenes 1–4 [1,4‐dichloro, ‐dibromo, ‐dimethoxy, and ‐bis(trimethylsilyl), respectively afforded the corresponding allylic hydroperoxides 1a–4a via regioselective ene reaction exclusively of the methyl hydrogens. The dichloro derivative 1 gave on photooxygenation in the presence of titanium tetraisopropoxide the desired epoxy alcohol 1b in fair yield (42%), along with the allylic alcohol 1c. The epoxy‐hydroxylation of the dibromo derivative 2 turned out to be problematic. Photooxygenation in the presence of Ti(OiPr)4 („one‐pot”︁ procedure) led to a complex product mixture, from which the allylic alcohol 2c, the dioxolane 2d, and the rearranged epoxy alcohol 5b were isolated. The structure of the latter was rigorously confirmed by an X‐ray analysis. Separate treatment of the allylic hydroperoxide 2a with Ti(OiPr)4 gave a similar complex product mixture.