The different approaches in which self-assembled monolayers (SAMs) have been applied in electroanalytical chemistry are reviewed. Three principal concepts have been used and can be categorized according to the mechanism of attachment of the monolayer to the electrode. These include the formation of covalent bonds between reactive organic molecules, such as chlorosilanes, with activated surfaces, the formation of lipid and bilayer lipid membranes that self-assemble on conductive surfaces and the adsorption of functionalized alkanes, e.g., alkanethiols, on well ordered surfaces. Systems for detecting inorganic, organic and biological species arc dcscribed and conclusions are drawn.