A novel synthetic methodology to diblock copolypeptides was developed by ring-opening polymerization (ROP) of N-carboxyanhydrides (NCAs) from α-ω-functionalized initiators combined with the Huisgen 1,3 dipolar cycloaddition (click chemistry). Poly(γ-benzyl-L-glutamate) (PBLGlu) and poly(trifluoroacetyl-L-Lysine) (PTFALys) containing either an azide or an alkyne functional group in α-position were first synthesized by ROP of the corresponding NCA at room temperature in DMF as a solvent, using appropriate ω-amino-containing α-alkyne and α-azido difunctional initiators. The copper(I)-catalyzed coupling reactions of α-azido-PBLGlu with the α-alkyne-PTFALys, on the one hand, and of the α-alkyne-PBLGlu with the α-azido-PTFALys, on the other hand were suitably accomplished in DMF. This afforded the targeted PBLGlu-b-PTFALys diblock copolypeptides possessing a triazole group in between the two blocks, as evidenced by SEC, IR, and NMR analysis. Block copolypeptides could be successfully purified by selective extraction with chloroform.