Novel renewable thermoplastic elastomers were synthesized by sequential polymerization of lysine-and itaconic acid-derived monomers. Ring-opening polymerization of lysine-based O-carboxyanhydride monomer using diethylene glycol as an initiator gave well-defined alpha,omega-dihydroxy functionalized lysine-derived polyesters. The M-n of these polyesters increased with the monomer conversion while retaining relatively narrow molecular weight distributions. Based on the successful controlled polymerization and esterification of alpha,omega-dihydroxy with 2-bromoisobutyryl bromide, the resultant BrPL-Br macroinitiator was used for the atom transfer radical polymerization of N-phenylitaconimide (PhII). Three poly(N-phenylitaconimide)-b-polyester-b-poly(N-phenylitaconimide) triblock copolymers were prepared containing 12225 mol% PPhII, as determined by H-1 NMR spectroscopy. The properties of the obtained triblock copolymer are evaluated as highperformance and renewable thermoplastic elastomer materials. (C) 2016 Wiley Periodicals, Inc.