The reduction of HNO 3 on Ag as a function of temperature in ultrahigh vacuum (UHV) is studied using Raman spectroscopy and thermal desorption-mass spectrometry (TDMS). Thin layers of molecular HNO 3 are stable on the surface below 150K, but are spontaneously reduced above 150K with concomitant time-dependent partial desorption of products. The asymmetric nitric oxide dimer, NONO, is observed as the sole reduction product that remains on the surface based on its distinctive Raman spectral signature. The mechanism of NONO formation from HNO 3 is proposed to occur through a multistep reduction of HNO 3 on the Ag surface starting from NO3- and proceeding stepwise through NO 2 and NO2- to NO, followed by combination to form NONO in a process catalyzed by a Lewis acid, oxidized Ag species. Desorption of the majority of surface species is largely complete by 210K.