A series of benzylic substituted P,N-ligands 1 and 2 have been synthesized. The Pd-complexes of these ligands show high catalytic activity and enantioselectivity in catalyzing the asymmetric Heck reaction. A dramatic switch in enantioselectivity is realized using ligands with and without substituents at the benzylic position of the ligand. Ligands 1 with H as the substituents offer products in (R)-configuration while ligands 2 with the methyl as substituents result in (S)-configuration products. In most cases high enantioselectivities are achieved. Density functional theory calculations on the reaction mechanism as well as X-ray analysis of 1a-PdCl2 and 2a-PdCl2 complexes provide a rational explanation for the above observations.