Our group and others have shown that HIR were ideal reagents for the selective functionalization of peptides. Herein, we report the successful copper-catalyzed alkynylation of azadipeptides (Scheme 1D). The mild reaction conditions allowed a broad functional group tolerance on the side chain of the peptides. Various types of alkynes could be transferred and undergo further transformations, enabling an easy access to functionalized azadipeptides.