The redox-active self-assembling system [Os(bpy)2LCl]+ (bpy = 2,2’-bipyridine; L = 4,4’-bipyridine (pypy),1,2-bis(4-pyridyl)ethane(dipyH2),trans-1,2-bis(4-pyridyl)ethylene(py=py), or 1,3-bis(4-pyridyl)-propane (dipy)) has been studied, using voltammetric methods, to investigate the dependence of the deposition potential, pH, and ionic strength on the thermodynamics of the self-assembling process. Repulsive electrostatic interactions are believed to give rise to (i) variations in the adsorption isotherms, (ii) shifts in E-degrees’ as a function of surface coverage, and (iii) differences in surface coverage between the reduced (Os(II)) and oxidized (Os(III)) forms of the complexes. A lowering of the pH of the deposition solution decreased the amount of adsorbate available for deposition so that lower unitary values were obtained. Finally, the ionic strength of the supporting electrolyte affected neither the adsorption equilibrium nor the thermodynamics of adsorption but did give rise to variation in the formal potential, probably due to charge screening effects.