A facile and phosgene-free synthetic route to poly(l-tryptophan) 2 by the polycondensation of N-phenoxycarbonyl-l-tryptophan 1 is described. The monomer 1 was synthesized via the carbamylation of tetrabutylammonium salt of L-tryptophan with diphenyl carbonate. The polycondensation proceeded smoothly at 60 °C in N,N-dimethylacetamide in the presence of amines (n-butylamine, diethylamine, and triethylamine) along with the elimination of phenol and carbon dioxide. The structural analysis of the obtained 2 by Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry revealed that n-butylamine or diethylamine was successfully incorporated into the chain end of the polypeptide. Furthermore, we have demonstrated the synthesis of a diblock copolymer by utilizing amine-terminated poly(ethylene glycol) as a source of the polyether segment. The chain length of the polypeptide segment was controlled by varying feed ratio between 1 and the amino group of poly(ethylene glycol). © 2013 Wiley Periodicals, Inc.