A bulk step-growth polymerization of multifunctional azides and alkynes through the copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is described The polymerization kinetics of two systems containing different diynes, bisphenol E diyne (BE-diyne)/bisphenol A bisazide (BA-bisazide) and tetraethylene glycol diyne (TeEG-diyne)/BA-bisazide, are evaluated by differential scanning calorimetry (DSC), shear rheology, and thermogravimetric analysis The effects of catalyst concentration on reaction kinetics are investigated in detail, as are the thermal properties (glass transition and decomposition temperatures) of the formed polymers. (C) 2010 Wiley Periodicals, Inc J Polym Sci Part A Polym Chem 48 4093-4102,2010