Cu-catalyzed hydrogen atom transfer (HAT) process is an efficient approach for the functionalization of benzylic C(sp 3 )-H bonds. Recently, Liu group and Stahl group achieved highly enantioselective benzylic C(sp 3 )-H bond functionalization for the C-C bond formation by using copper catalyst and N-fluorobenzenesulfonimide (NFSI). 10 However, when this catalytic system is used for benzylic C-N bond formation, racemic products are often obtained (Scheme 1C). 11,12 Thus new catalytic system is need to be developed for the enantioselective intermolecular C(sp 3 )-H bond amination through hydrogen atom transfer (HAT) process. Here, we report a highly enantioselective intermolecular benzylic C(sp 3 )-H bond amination by using chiral cationic copper catalyst and the oxidant di-tert-butyl peroxide (DTBP) (Scheme 1D).