A Cu-catalyzed highly diastereo- and enantioselective methylboration of diverse heterocyclic compounds including 1,2-dihydroquinolines, 2H-chromenes and 2H-thiochromenes providing the corresponding organoboron compounds bearing two adjacent chiral centers with excellent diastereoselectivities (dr up to >99 : 1) and enantioselectivities (up to 99.9% ee) has been realized for the first time. This method provides an efficient and highly enantioselective approach for the synthesis of chiral organoboron compounds and their derivatives containing heterocyclic structures.