Up to now, synthetic polymers and biomacromolecules have been grafted or assembled onto the convex surface of carbon nanotubes (CNTs) via covalent bonds or chemisorptions. In this research, poly(L-lactide-co-epsilon-caprolactone)-functionalized multiwalled carbon nanotubes (MWCNT-OH-g-PCLA)s are synthesized by in situ ring-opening copolymerization of L-lactide (LA) and epsilon-caprolactone (CL) using stannous octanoate and hydroxylated MWCNTs (MWCNT-OHs) as the initiating system. The pristine MWCNTs are modified to possess carboxyl groups and then hydroxyl groups. MWCNT-OHs are used as coinitiators to polymerize LA and CL by the surface-initiated ring-opening polymerization. The FT-IR spectra, SEM and TEM micrographs revealed that the PCLA grafted form the sidewall of MWCNTs strongly. The TGA analysis indicates that about 75 wt% of functionalized MWCNTs with PCLA belongs to grafted PCLA and the remaining 25 wt% to the initial MWCNT-OH. (C) 2009 Elsevier B.V. All rights reserved.