This work reports the electrosynthesis of 7,7′-Bi(2-methyl-8-thia-1,3,3a1,4-tetraazacyclopenta[def]fluorene), as a novel coating derivative on a platinum grid through the anodic oxidation of 3-(4-fluorophenyl)-2-methyl-[1,2a]benzimidazolo-1,3,5-triazine-4-thione, in an acetonitrile solution.3-(4-fluorophenyl)-2-methyl-[1,2a]benzimidazolo-1,3,5-triazine-4-thione was crystallography characterized and electrochemically studied for the first time using the pentiodynamic, and potentiostatic approaches. Cyclic voltammetry on a platinum disk reveals a succession of three irreversible anodic waves that the first step was concerned by the potentiostatic electrolysis on a platinum grid, leading to an electrodeposited symmetrical dimer of tetracyclic units. Through the electrochemical investigations, conjointly to the quantum chemical calculations, a CC bond formation between the aromatic rings of two starting molecules was suggested, as well as CS bonds establishment through intramolecular cyclization, in the CC ortho position of the benzimidazole ring, and two fluorobenzene molecules elimination.