The adsorption of nitrogen species, in neutral electrolyte solutions, onto boron-doped diamond (BDD) electrode surfaces from dissolved NO2, NO, and N2O gases was induced at 0 V/SCE. Modified BDD electrode surfaces showed a different electrochemical response toward the hydrogen evolution reaction than did a nonmodified electrode surface in electrolyte base solution. The formation of molecular hydrogen and nitrogen gaseous species was confirmed by the online differential electrochemical mass spectrometry (DEMS) technique. Among the three nitrogen oxides gases, NO2 substantially modifies the electrolyte via hydrolysis leading to the formation of NO3 and its adsorption on the BDD electrode surface. The BDD/(NO3-) interface was the only N2O and N-2 species generating system.