The modification of the glassy carbon surface in contact with AgNOJ solution has been studied using X-ray diffraction and Brunauer, Emmett and Teller (BET) surface analysis methods. The deposition of metallic silver, confirmed by X-ray analysis, affected the pore system resulting in a decrease of surface area and pore volume. The thermal decomposition of the surface oxide species resulting in desorption of H 2 0 , CO and COz as major gas products has been studied using a temperature-programmed desorption method combined with a mass spectrometric analysis of the desorbed gases. The desorption energies have been calculated using a peak position method. It has been concluded that the silver deposition on the glassy carbon surface contributes to the increased stability of surface oxide species.