Self-assembled monolayers (SAMs) of straight-chain alkylthiols and alkylamines (CnH2n+1 SH/NH2: n = 10, 12, 16, 18) are adsorbed from solution onto the electrochemically reduced (oxide-free) surface of 316L stainless steel. The SAMs were characterized using X-ray photoelectron spectroscopy. contact angle measurements and Fourier transform infrared spectroscopy. While thiol and (to a lesser extent) amine anchored coatings have been reported on iron and other metals, this work constitutes a new approach to the surface modification of stainless steel. This coating approach was further extended by depositing alpha,omega-hydroxythiols to create a thin film with a hydroxyl-rich surface. This new surface was then used to anchor a siloxane-based second layer.