Self-assembled molecular films were formed on the electrode surfaces of glassy carbon (GC), platinum (Pt), gold, silver and indium-tin oxide in aqueous electrolyte solutions of N-docosyl-N'-methyl viologen (C22VC1). The temperature dependence of voltammetric responses showed a higher stability with higher surface coverage and with a Pt than a GC surface. Charge transfer reactions of the solution redox species of Ru(NH3)(6)(3+) and Fe(CN)(6)(4-) at the irreversibly self-assembled C22VC1\GC interface were found to take place by an interplay of direct penetration of solution species through the self-assembled molecular layer of C22VC1 and of cross reaction between solution and surface bound redox agents.