Abstract: Polypeptides are a type of natural polymers that are composed of α-amino acids and are connected with peptide bonds, displaying a variety of important biological functions. The ring-opening polymerization of N-carboxyanhydride is the most convenient approach to synthesize polypeptides and has been widely used in diverse fields for different applications. Conventional NCA polymerization is very sensitive to water and the reaction generally requires strictly dried solvents and inert atmosphere in a glovebox. The slow reaction of NCA polymerization and the low stability of NCA monomer together result in side reactions during polymerization and the difficulty in preparing polypeptides with high molecular weight. These unsolved problems have hindered the development of NCA chemistry and studies of resulting polypeptides. Recently, Prof. Liu's group at East China University of Science and Technology reported a Lithium Hexamethyldisilazide(LiHMDS) initiated rapid ring opening polymerization of NCA. The novel polymerization is not sensitive to water and can even be operated in open vessels without using glovebox. This NCA polymerization can be used to prepare polypeptides with high molecular weight and defined secondary structures. Such a living NCA polymerization also enables convenient terminal functionalization of the polypeptides.