The copper-catalyzed hetero-allylic asymmetric alkylation ( h-AAA) of functionalized Grignard reagents that contain alkene or alkyne moieties has been achieved with excellent regio- and enantioselectivity. The corresponding alkylation products were further transformed into a variety of highly functionalized cyclic and bicyclic alcohols with excellent control over the chemo-, regio-, and stereoselectivity.