L-Proline is the only, out of 20 essential, amino acid that contains a cyclized substituted a-amino group (is formally an imino acid), which restricts its conformational shape. The synthesis of well-defined homo-and copolymers of L-proline has been plagued either by the low purity of the monomer or the inability of most initiating species to polymerize the corresponding N-carboxy anhydride (NCA) because they require a hydrogen on the 3-N position of the five-member ring of the NCA, which is missing. Herein, highly pure L-proline NCA was synthesized by using the Boc-protected, rather than the free amino acid. The protection of the amine group as well as the efficient purification method utilized resulted in the synthesis of highly pure L-proline NCA The high purity of the monomer and the use of an amino initiator, which does not require the presence of the 3-N hydrogen, led for the first time to well-defined poly(L-proline) (PLP) homopolyrners, poly(ethylene oxide)-b-poly(L-proline), and poly(L-proline)-b-poly(ethylene oxide)-b-poly(L-proline) hybrids, along with poly(gamma-benzyl-L-glutamate)-b-poly(L-proline) and poly(Boc-L-lysine)-b-poly(L-proline) copolypeptides. The combined characterization (NMR, FTIR, and MS) that results for the L-proline NCA revealed its high purity. In addition, all synthesized polymers exhibit high molecular and compositional homogeneity.