Copper(0)-catalyzed one-pot reaction combining living radical polymerization and click chemistry was investigated. By precisely tuning reaction time, three novel well-defined polymers with different degree of carboxyl substitution, poly(propargyl methacrylate) (PPgMA), poly(1-(4-carboxyphenyl)-[1,2,3]triazol-4-methyl methacrylate) (PCTMMA), and poly(1-(4-carboxyphenyl)-[1,2,3]triazol-4-methyl methacrylate-co-propargyl methacrylate) (PCTMMA-co-PPgMA) were selectively obtained via Cu(0) powder/N,N,N',N?,N?-pentamethyldiethylenetriamine (PMDETA) cocatalyzed LRP and click chemistry. In addition, gel permeation chromatography and 1H NMR analysis in conjunction with FTIR spectroscopy elucidate that one-pot process undergoes three steps due to a pronounced rate enhancement of click reaction: (1) generating new monomer, 1-(4-carboxyphenyl)-[1,2,3]triazol-4-methyl methacrylate (CTMMA); (2) copolymerization of two monomers (CTMMA and PgMA); (3) building homopolymer PCTMMA. Surprisingly, in contrast to typical Cu(I)-catalyzed atom transfer radical polymerization (ATRP), copper(0)-catalyzed one-pot reaction showed high carboxylic acid group tolerance. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012