The odtadecanethiol (ODT) was dispersed in aqueous solution with different surfactants, and then self-assembled monilayers (SAMs) were prepared on the surface of silver. The anticorrosion function and adsorption behavior of ODT SAMs on the silve surface was investigated by means of polarization curve, AC impedance and circular voltammetric methods. The results show that ODT is easy to form dense and stable SAMs on the surface of silver. It effectively suppresses silver anodic oxidation process and cathodic reduction process, and changes the surface electric double layer structure of the silver electrode. The results from electrochemical measurement indicate that the corrosion resistance of silver is improved by the ODT SAMs. Adsorption of the ODT SAMs follows the Langmuir’s adsorption isotherm, and the adsorption mechanism is typical chemisorption