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)(3)Si(OMe)(3) (1, R-F = C5F11), containing an embedded amide between the perfluoroalkyl chain and the syloxanic moiety, and R-F(CH2)(2)Si(OEt())3 (2, R-F = C6F13). Subsequently, Au nanoparticles (Au-Nps) introduction in the obtained systems was carried out by controlled immersion into a solution of citrate-stabilized AuNps. The physico-chemical properties of the target materials were thoroughly investigated by using various complementary techniques. Finally, the application of such systems as catalysts for methanol electro-oxidation under alkaline conditions was investigated, revealing the synergistical role played by FAS and Au-Nps in promoting a remarkable electrocatalytic activity. (C) 2015 Elsevier B.V. All rights reserved.