In this study, a series of linear poly(triazole)s (PTAs) were successfully synthesized by the metal- and solvent-free, thermal click polymerization of diazide and dialkyne (A2 + B2) monomers. All click polymerizations proceeded smoothly at 80 degrees C in an open atmosphere without protection from oxygen and moisture. After being polymerized for 36 h, the crude polymer was further fractionated into three fractions using a multistep precipitation method. By selectively choosing precipitating agents, this process produced poly(triazole) fractions with low polydispersity index (<1.30). The resulting PTAs are soluble in common organic solvents and stable at a temperature up to 320 degrees C. Furthermore, the methyl benzoate moieties in the main chain can serve as useful building blocks for further postpolymerization functionalization, yielding 1,2,4-triazole derivatives. This functionalization strategy offers potential for the development of novel triazole-based materials. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012