A solvent- and chromatography-free, non-hazardous green protocol for the synthesis of 2-alkylbenzimidazoles has been developed under neutral conditions with water as the only by-product. Activated alumina balls, which have been shown previously to assist in amidation reaction, also catalyze very successfully the condensation of benzene-1,2-diamines with carboxylic acids to produce the corresponding benzimidazoles. This methodology is also applicable to susceptible side chains possessing an amide functionality.