Metal/organosilane/oxide sandwich structures were prepared via a two-step self-assembly method.First, indium tin oxide (ITO) substrates were functionalized with the following fluoroalkylsilanes (FAS):RFC(O)N(H)(CH2)3Si(OMe)3(1, RF= C5F11), containing an embedded amide between the perfluoroalkylchain and the syloxanic moiety, and RF(CH2)2Si(OEt)3(2, RF= C6F13). Subsequently, Au nanoparticles(AuNPs) introduction in the obtained systems was carried out by controlled immersion into a solution ofcitrate-stabilized AuNPs. The physico-chemical properties of the target materials were thoroughly inves-tigated by using various complementary techniques. Finally, the application of such systems as catalystsfor methanol electro-oxidation under alkaline conditions was investigated, revealing the synergisticalrole played by FAS and AuNPsin promoting a remarkable electrocatalytic activity.