Benzimidazoles are versatile heterocyclic compounds with significant applications in various fields including natural products and pharmaceuticals. They are privileged scaffolds in bioactive molecules with pharmaceutical relevance. In this study, we developed a novel method for synthesizing benzimidazoles from azobenzene and ketones via C–C bond cleavage between the α carbon and the carbonyl carbon of the ketone. By employing ketones, previously unexplored substrates, this strategy broadens the synthetic toolbox for benzimidazole construction, offering greater flexibility in heterocycle synthesis.