Surface chemistry is a significant field of research, especially for the preparation of organic-inorganic hybrid materials in which nearly every atom is anchored at the interface. Herein we report on the functional binding agents (FBAs), Mg(OH)(2) or Co(OH)(2)-Mg(OH)(2)-Co(OH)(NO3), as efficient tools for functionalising surfaces, whereby the morphology and growth of the organic-inorganic coating can be varied by varying the interfacial composition to achieve improved functionality. To demonstrate the potential of this strategy, we combine plasma electrolytic oxidation (PEO) and a two-step dip chemical coating (DCC) technique to deliver multi-layered constructions of several chemical compositions comprising inorganic and organic components. A novel single layer of FBAs is fabricated on the rough inorganic coating through chemical treatment via DCC, transforming it into a binding site for primary clusters of 2-mercaptobenzimidazole (MBI) molecules. Thus, FBAs form coordination complexes with organic molecules, which grow on FBA surfaces. Finally, electrochemical measurements reveal that the self-assembly of organic-inorganic hybrid heterostructures appreciably suppresses metal oxidation and oxygen reduction, due to a synergistic effect arising from the combination of FBAs with organic and inorganic coatings. (C) 2020 Elsevier Inc. All rights reserved.