The Diels-Alder reaction as a click reaction strategy is applied to the preparation of well-defined polycarbonate (PC)-block copolymers. A well-defined -anthracene-terminated polycarbonate (PC-anthracene) is prepared using 9-anthracene methanol as an initiator in the ring opening polymerization of benzyl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate in CH2Cl2 at room temperature for 5 h. Next, a well-defined -furan protected maleimide-terminated-poly(ethylene glycol) (PEG11-MI or PEG37-MI), -poly(methyl methacrylate) (PMMA26-MI), and -poly(epsilon-caprolactone) (PCL27-MI) were clicked with the PC-anthracene at reflux temperature of toluene to yield their corresponding PC-based block copolymers (PC-b-PEG, PC-b-PMMA, and PC-b-PCL). The homopolymer precursors and their block copolymers were characterized by using the GPC, NMR and UV analysis. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 2252-2259