By using either NH(2)-functionalized linear/4-arm star poly(ethylene oxide) or NH(2)-TEMPO initiator, the following novel polymer/polypeptide hybrids (macromolecular chimeras) of poly(ethylene oxide), PEO and poly(N-vinyl pyrrolidone), PNVP, were synthesized: PEO-b-(PBLG or PBLL), PEO-b-PBLL-b-PBLG, 4-arm star copolymer (PEO-b-PBLG)(4), PNVP-b-PBLG-b-PBLL, where PBLG is poly(gamma-benzyl-L-glutamate) and PBLL, poly(tert-butyloxycarbonyl-L-lysine). The amino-groups are used for the ring opening polymerization (ROP) of alpha-amino acid carboxyanhydrides (NCAs), while TEMPO was employed for the polymerization of NVP. Molecular characterization revealed the high molecular weight and compositional homogeneity of the macromolecular chimeras prepared. The success of the synthesis was based on the recently developed living ROP of NCAs and controlled/living TEMPO polymerization, using high vacuum techniques. (C) 2008 Elsevier Ltd. All rights reserved.