A facile and sustainable electrochemical synthetic strategy for phenyl benzimidazoles has been developed using a ferrocene-based electrocatalyst anchored on Toray carbon paper (TCP) coated with conducting polymeric film. The developed electrode was used for the electrochemical dehydrogenative cyclization reaction of o-phenylene diamine and benzaldehyde using lithium perchlorate/acetonitrile as electrolyte. The surface characteristic properties of the developed electrode were characterized by FESEM, Optical profilometer and X-ray photoelectron spectroscopy. Electron transfer mechanism of the anchored ferrocene-based electrocatalyst was thoroughly studied. To determine the efficacy of the catalyst, the electron transfer coefficient (0.5) and apparent rate constant 41.4 s⁻¹ were determined. The cyclic voltammetry studies reveal that the electrochemical oxidation peak for the synthesis of benzimidazole occurs at 0.48 V. The formation of the product was confirmed by Gas chromatography and Nuclear Magnetic Resonance spectroscopy. A comparison chart is presented for the green metrics and sustainability of the present strategy with other electrochemical approach.