This article presents the application of an adhesion promoting highly crosslinked ultrathin organic-inorganic hybrid layer applied to steel which promotes the subsequent joining process based on plastic deformation. The tensile shear results show that a significant increase of the bond strength between low-alloy steel (DC04) and aluminum (AW1050A H111), upon cold-pressure welding (CPW), could be achieved. Electrografting of an ultra-thin film of 1,2-bis(triethoxysilyl)ethane (BTSE) films on the steel surface was done from ethanolic solutions containing zinc ions. Based on surface spectroscopic analysis it is shown that silanol moieties present in the organosilane deposits can form stable chemical bonds with both the iron oxide covered steel and the aluminum oxide covered aluminum alloy. The successful modification of metal oxide surfaces with BTSE has been demonstrated via SEM-EDX, AFM, PM-IRRAS, and XPS measurements. In addition, electrochemical analysis of the BTSE:Zn films showed that the films lead to very good corrosion properties even at low thicknesses.