In this work, we examined the relationship between the anticorrosion behavior and the structure of the cysteamine/L-cysteine layer-by-layer coating on the copper surface via the self-assembled monolayers (SAMs) technique with electrochemistry and surface-enhanced Raman scattering (SERS) spectroscopy. SERS results elucidated the layer-by-layer adsorption mechanism of cysteamine/L-cysteine at the copper surface. Electrochemical investigations explored the inhibition behavior of cysteamine/L-cysteine for copper from corrosion with a high protection efficiency of 91.4%. (C) 2014 Elsevier B.V. All rights reserved.