A disparate polymerization technique is utilized for preparing versatile block copolymers from poly(trimethylene carbonate) (poly(TMC)). In this study, 4-(chloromethyl)benzyl alcohol (CBA) is used for the disparate polymerization. The hydroxyl group of CBA is involved in ring-opening polymerization and the benzyl chloride group is involved in incorporating dithiocarbamate for pseudo-living radical polymerization. First, TMC is polymerized from the hydroxyl group of CBA by using an organocatalyst. The benzyl chloride group in CBA is modified using a dithiocarbamate, and then vinyl and methacrylate monomers are polymerized by photo-driven pseudo-living radical polymerization. The resulting block copolymers are versatile and the molecular weight distribution is reasonably narrow. In the present study, N-isopropylacrylamide, acrylamide glycolic acid, and 2-hydroxyethyl methacrylate are used for the disparate polymerization. The resulting block copolymers could be well dissolved in water by incorporation of hydrophilic segment into hydrophobic poly(TMC). The solution property is characterized in terms of hydrophobic domain formation and phase transition under ambient conditions. Moreover, enzymatic degradation is evaluated by using a copolymer-coated substrate. The block copolymer synthesis technique is considerably versatile, and the resulting polymer function can be freely designed. The disparate polymerization technique is a promising approach that provides universal materials for integrating biodegradable polyesters and functional polymers. (c) 2008 Elsevier Ltd. All rights reserved.