Surface nitrate (NO3(-)) species on the Ag/Al2O3 play an important role in the selective catalytic reduction (SCR) of NOx. In this study, the formation and configuration of surface nitrate NO3(-)(ads) species on Ag/Al2O3 and Al2O3 in the oxidation of NO have been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations. Different nitrates species (bridging, bidentate and monodentate) were observed by in situ DRIFTS and validated by DFT calculations results. Attention was especially focused on the proposal of two different bidentate nitrates species (a normal bidentate and an isolated bidentate). In addition, the thermal stability of different surface nitrate species was discussed based on the adsorption energies calculations, DRIFTS, and temperature-programmed desorption (TPD) results. It was suggested that the decomposition and desorption of the surface nitrate species could be controlled by kinetics.