Stainless steel 316L is a widely used biomaterial substrate whose biocompatibility could be improved by surface modification. As a first step in this process, self-assembled monolayers of octanoic acid, octadecylcarboxylic acid, 16-hydroxyhexadecanoic acid, 12-aminododecanoic acid, and 1,12-dodecane dicarboxylic acid have been formed on the native oxide surface of stainless steel 316L by a simple, one-step solution deposition method. The ordering, close-packing, and coverage of the monolayers formed were characterized by diffuse reflectance infrared spectroscopy, contact angle measurements, and atomic force microscopy. The same procedure was applicable for all long alkyl chain carboxylic acids. This process formed chemically and mechanically stable monolayers. These carboxylic acids formed a bidentate bond with the stainless steel substrate. Robust chemical attachment of the acids to stainless steel through a simple process provides a stepping stone to improving the biocompatibility of stainless steel 316L.