Fe-catalyzed borylation of ketones to access tertiary α-hydroxyboronates has been demonstrated. In this transformation, commercially available FeBr2 was used as the catalyst, alcohols have been added to accelerate the transformation and avoid the side reaction. Various aliphatic ketones with different functional groups have been converted into tertiary α-hydroxyboronates. This transformation showed a particular tolerance for ketones with steric hinderance, which was distinguished from the traditional Cu catalyst. A gram scale reaction was also available. The alcoholic C—O functionalizations based on α-hydroxyboronates have been realized to access tertiary alkyl boronic esters, gem-diborylalkanes and gem silylborylalkanes.