Herein, we disclose an asymmetric alkylation of an α-C(sp3) bond of glycine derivatives proceeding through synergistic copper/photoredox catalysis. It is worth noting that this work represents the first example of an asymmetric transformation induced by the challenging 1,2-HAT process of amidyl radicals. This protocol is characterized by good yields, moderate to excellent enantioselectivities and simple operation procedures, providing an attractive strategy for the synthesis of biologically valuable α,β-diamino acids.