A method is proposed for characterization of the electrostatics of self-assembled monolayers (SAMs). The method is based on the extraction of the metal's effective work function in metal-oxide-semiconductor capacitors, where the SAM is positioned at the metal-oxide interface. Hexyltrichlorosilane molecules assembled on SiO 2 are used as a model system for this method. A band offset of 0.5 ± 0.15 eV is observed in the SAM sample when compared to a reference with no molecules. Spectroscopy is employed to confirm the presence of silane anchoring groups after metal deposition.