In this study, an alternative synthesis of polybenzimidazoles was performed with aromatic hydroxamoyl chloride. In contrast to the literature, polybenzimidazoles were obtained through the reaction of hydroxamoyl chlorides with 3,3'-diaminobenzidine or 1,2,4,5-tetraaminobenzene. The characterization of the polymers was performed with Fourier transform infrared, H-1-NMR, elemental analysis, LC mass spectrometry, and differential thermogravimetry/thermogravimetric analysis. Finally, the adhesion, corrosion resistance, and conducting properties of the synthesized polymers were examined. (C) 2008 Wiley Periodicals, Inc.