We report a stereoselective and site-specific allylic alkylation of Schiff base activated amino acids and small peptides via a Pd/Cu dual catalysis. A range of noncoded alpha,alpha-dialkyl alpha-amino acids were easily synthesized in high yields and with excellent enantioselectivities (up to >99% ee). Furthermore, a direct and highly stereoselective synthesis of small peptides with enantiopure alpha-alkyl or alpha,alpha-dialkyl alpha-amino acids residues incorporated at specific sites was accomplished using this dual catalyst system.