Surface enhanced Raman scattering (SERS) spectrum of the 2-amino-5-(4-pyridinyl)-1,3,4-thiadiazole (4-APTD) on the silver surface was recorded and assigned with the help of B3LYP/6-311G** method. SERS result explored that 4-APTD molecule with a tilted orientation anchored at the silver surface via N-12, S-1 and C-2 atoms. In situ SERS spectroelectrochemical experiment indicated 4-APTD molecule experienced an intermediate adsorption process of its thiadiazole ring moiety with the vertical orientation at the surface before the 4-APTD molecule detached completely from the surface as the potential applied at -1.3V vs. SCE. Electrochemical impedance spectroscopy (EIS) and polarization experiments exhibited the sound anticorrosive effect of the 4-APTD film on silver surface with an efficiency of 89.5%. (C) 2011 Elsevier B.V. All rights reserved.