A versatile platform for incorporation of various amines and related derivatives into α-amino acid derivatives through α-amino C-H bond functionalization has been developed. Through selective activation of α-amino C-H bonds of tertiary amines and anilines with organic acridinium photocatalysts and subsequently nonactivated amines using a direct HAT catalyst, this approach allows highly selective and efficient synthesis of various asymmetric α-amino acid derivatives. The disclosed protocols are tolerant of a variety of orthogonal functional groups as well as versatile nitrogen protecting groups. The synthetic utility of the developed transformation will ease access to more structurally diverse α-amino acid derivatives as an entry to novel biologically relevant natural products, pharmaceutical agents, agrochemicals, and materials.