A Pd(II)-catalyzed enantioselective C-H cross-coupling of benzylamines via kinetic resolution has been achieved using chiral mono-N-protected alpha-amino-O-methyl-hydroxamic acid (MPAHA) ligands. Both chiral benzylamines and ortho-arylated benzylamines are obtained in high enantiomeric purity. The use of a readily removable nosyl (Ns) protected amino group as the directing group is a crucial practical advantage. Moreover, the ortho-arylated benzylamine products could be further transformed into chiral 6-substituted 5,6-dihydrophenanthridines as important structural motifs in natural products and bioactive molecules.