We prepared well-defined diblock copolymers of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) blocks and biodegradable poly(D,L-lactide) blocks by combination of reversible addition-fragmentation chain transfer radical (RAFT) polymerization and ring-opening polymerization. alpha-Hydroxyl, omega-dithiobenzoate thermoresponsive polymers were synthesized by RAFT polymerization using hydroxyl RAFT agents. Biodegradable blocks were prepared by ring-opening polymerization Of D,L-lactide initiated by a-hydroxyl groups of thermoresponsive polymers, which inhibit the thermal decomposition of omega-dithioester groups. Terminal dithiobenzoate (DTBz) groups of thermoresponsive blocks were easily reduced to thiol groups and reacted with maleimide (Mal). In aqueous media, diblock copolymer products formed surface-functionalized thermoresponsive micelles. These polymeric micelles had a low critical micelle concentration of 22 mu g/L. In thermoresponsive studies of the micelles, hydrophobic DTBz-surface micelles demonstrated a significant shift in lower critical solution temperature (LCST) to a lower temperature of 30.7 degrees C than that for Mal-surface micelles (40.0 degrees C). In addition, micellar LCST was controlled by changing bulk mixture ratios of respective heterogeneous end-functional diblock copolymers. Micellar disruption at acidic condition (pH 5.0) was completed within 5 days due to hydrolytic degradation of PLA cores, regardless of showing a slow disruption rate at physiological condition. Furthermore, we successfully improved water-solubility of hydrophobic drug, paclitaxel by incorporating into the micellar cores. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7127-7137, 2008