In this study, poly(vinylbenzylchloride) (PVBC) was produced by free-radical polymerization of 4-vinylbenzylchloride, and then it was functionalized with 3-amino-1,2,4-triazole (ATri) and 1H-1,2,4-triazole (Tri). The composition of the polymers was verified by elemental analysis, and the structure was characterized by Fourier transform infrared and C-13-nuclear magnetic resonance spectra. PVBC was modified by ATri with 68% and Tri with 50% yield. The polymers were doped with trifluoromethanesulfonic acid ( TA) at various molar ratios, X 0.5, 1, 2, and 3 with respect to aminotriazole and triazole units. Proton transfer from TA to the triazole rings was proved with Fourier transform infrared spectroscopy. Thermogravimetric analysis showed that the samples are thermally stable up to approximately 200 degrees C. Differential scanning calorimetry results illustrated the homogeneity of the materials. Under anhydrous conditions, PVBCATri3TA and PVBCTri3TA showed highest proton conductivity of 0.086 and 0.042 S/cm, respectively. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4974-4980, 2010