Block copolypeptides, which combine the self-assembly of block copolymers and the highly ordered 3D structures of proteins, are potential candidates for novel supramolecular structures and biotech applications, such as biosensors, tissue engineering, and selective drug delivery. The synthesis of model block copolypeptides through living nucleophilic/basic polymerization of alpha-amino acid N-carboxyanhydrides (NCAs) has been a challenge for more than fifty years, most probably due to traces of impurities in the system. This problem has been overcome, using high vacuum techniques in order to create and maintain the conditions necessary for the living polymerization of NCAs with primary amines. This method is a general one and opens avenues leading to novel, well-defined polypeptides with various architectures.