Siloxane-anchored self-assembled monolayers have been obtained on stainless steel. Initially the surface of the material was treated with tetraalkylorthosilicate in order to obtain a thin layer of SiO2 (<3 nm). This layer effectively anchors the subsequent attachment of alkyl trialkoxysilanes like octadecyltrimethoxysilane. Some of the versatility of this approach was demonstrated by depositing thioacetate (TA)-hexadecyltrimethoxysilane on SiO2-modified stainless steel and forming a TA functionalized film. In situ oxidation of the TA groups yielded a sulfonate-functionalized surface that was used to promote deposition of an adherent, pore-free, TiO2 layer from aqueous solution onto the stainless steel substrate.