Organic layers chemically grafted on silicon offer excellent interfaces that may open up the way for new organic–inorganic hybrid nanoelectronic devices. However, technological achievements rely on the precise electronic characterization of such organic layers. We have prepared ordered grafted organic monolayers (GOMs) on Si(111), sometimes termed self-assembled monolayers (SAMs), by a hydrosilylation reaction with either a 7-carbon or an 11-carbon alkyl chain, with further modification to obtain amine-terminated surfaces. X-ray photoelectron spectroscopy (XPS) is used to determine the band bending (∼0.3 eV), and ultraviolet photoelectron spectroscopy (UPS) to measure the work function (∼3.4 eV) and the HOMO edge. Scanning tunneling microscopy (STM) confirms that the GOM surface is clean and smooth. Finally, conductive AFM is used to measure electron transport through the monolayer and to identify transition between the tunneling and the field emission regimes. These organic monolayers offer a promising alternative to silicon dioxide thin films for fabricating metal–insulator–semiconductor (MIS) junctions. We show that gold nanoparticles can be covalently attached to mimic metallic nano-electrodes and that the electrical quality of the GOMs is completely preserved in the process.