A brief, practical catalytic process for the production of optically active γ-functionalized alcohols from relevant alkenes has been developed by using a robust Mn(III)/air/(Me 2 SiH) 2 O catalytic system combined with lipase-catalyzed kinetic resolution. This approach demonstrates exceptional tolerance toward proximal functional groups present on alkenes, enabling the achievement of high yields and exclusive enantioselectivity. Under this sequential catalytic system, the chiral alkene precursors can also be converted into γ-functionalized alcohols and related acetates as separable single enantiomers.