A new one-step electrochemical approach for the localized generation of diazonium cations in the diffusion layer of an electrode by taking advantage of the electrocatalytic properties of the electrode for the formation of the diazotization agent (nitrite) is proposed. Once nitrite anions are formed by electrocatalytic reduction of nitrate, they immediately react with an arylamine to produce the corresponding diazonium cations, which can be electrochemically readily reduced at the electrode surface. By this method, spontaneous modification of the electrode surface can be avoided. Furthermore, because the potential of the electrochemical nitrate reduction depends strongly on the nature of the electrode material, we also demonstrate that selective grafting can be achieved on a surface, which consists of two different materials: copper-gold or copper-glassy carbon substrates.