The adsorption of aniline on a silver mirror was studied by surface-enhanced Raman scattering (SERS) spectroscopy and density functional theory (DFT) calculation methods. The normal Raman and SERS spectra of pure aniline liquid and its solutions were recorded by a micro-Raman spectrometer with excitation at 514.5 nm. Orientation of the aniline molecule adsorbed on the Ag mirror is discussed. The results indicate that pure aniline is adsorbed on the surface of the Ag mirror with a tilted orientation. The conformer with the nitrogen atom interacting with the metal surface would be dominant. DFT calculations further confirm the experimental results that charge transfer (CT) takes place from the highest occupied molecular orbital(HOMO) of aniline to the singly occupied molecular orbital (SOMO) of the silver surface. In this paper, the frontier molecular orbital theory has been successfully used to explore the interaction between the aniline molecule and the silver surface. Copyright © 2011 John Wiley & Sons, Ltd.