The modification of the glassy carbon surface in contact with AgNO3 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 H2O, CO and CO2 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.