The regiospecific Cα–Cβ cleavage of allylic alcohols under modified aerobic Mukaiyama hydration conditions is presented. The new methodology can be regarded as an equivalent of a two‐step process, a typical hydration of the parent allylic alcohol followed by a 1,2‐diol cleavage. A broad scope of substrates, both cyclic and acyclic, are applicable, thus introducing substantial structural modification to the core, especially of the former type of substrates. Mechanistic investigation of the reaction reveals the importance of the nearby hydroxyl group for the deviation from the typical Mukaiyama hydration pathway.