This paper describes the covalent attachment of various organic molecules to the hydrogenterminated surface of porous silicon using alcohols and Grignard reagents. With alcohols, the chemical reaction forms Si-O-C attachments to the silicon substrate and requires modest heating (40–70 °C). With Grignard reagents, the reaction proceeds at room temperature and forms a covalent film that is attached by Si-C bonds to the silicon support. Evidence for these reactions is provided by infrared and x-ray photoelectron spectroscopies.