Herein, a novel hydroboration of epoxides catalyzed by zinc- and aluminum- based catalysts was presented here for the efficient and selective synthesis of primary alcohols. This reaction was operationally simple and environmentally friendliness. Furthermore, it was found that various primary alcohols could be obtained with high yield and selectivity under mild conditions by using stoichiometric HBpin as boron source. Mechanistic studies and control experiments were proposed, leading to the consequence that zinc- and aluminum- based catalysts accelerated the isomerization of epoxides to form aldehydes, which were further hydrogenated to organoboron compounds by metal catalysts and HBpin, and subsequently hydrolyzed to primary alcohols.