In this work, poly(4-vinylbenzylboronic acid-co-4(5)-vinylimidazole) (poly(4-VBBA-co-4-Vim)) copolymers were synthesized by free-radical copolymerization of the monomers 4-VBBA and 4-Vim at various monomer feed ratios. The copolymers were characterized by H-1 MAS NMR and B-11 MQ-MAS NMR methods and the copolymer composition was determined via elemental analysis. The membrane properties of these copolymers were investigated after doping with phosphoric acid at several stoichiometric ratios. The proton exchange reaction between acid and heterocycle is confirmed by FTIR. Thermal properties of the samples were investigated via thermogravimetric analysis (TGA) and Differential scanning calorimetry (DSC). The morphology of the copolymers was characterized by x-ray diffraction, XRD. The temperature dependence of proton conductivities of the samples was investigated by means of impedance spectroscopy. Proton conductivity of the copolymers increased with the doping ratio and reached to 0.0027 S/cm for poly(4-VBBA-co-4-Vim)/2H(3)PO(4) in the anhydrous state. The boron coordination in the copolymer was determined by B-11 MQ-MAS experiment and the coexistence of three and four coordinated boron sites was observed. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1267-1274, 2009