A study was conducted to demonstrate the use of the RAFT CTA for the covalent conjugation of the thermally responsive polymer, poly(diethylene glycol methyl ether methacrylate) (PDEGME-MA) to the collagen-like peptide equipped with amine groups at both the N- and C-termini. It was observed that after de-protection of the peptide sequence, the synthesized triblock structure showed expected assembly into collagen-like triple helices in aqueous solution. The stimuli-responsive polymer, PDEGMEMA, was synthesized through RAFT polymerization using pentafluorophenyl-(4-phenylthiocarbonylthio-4- cyanovalerate) as CTA following a standard polymerization procedure. It was observed that the approach could be applied to various peptides with addressable amine groups and to a variety of synthetic polymers amenable to synthesis by RAFT polymerization using the functional CTA.