The oxidation of aromatic primary amines was studied in natural, basic or acidic medium catalysed by silver(I). Various aromatic amines could be oxidized to corresponding azoderivatives. Electron withdrawing substituents were found to slow down the reaction and strong substituents did not allow the reaction to proceed. The presence of electron donating substituents such as –CH3 on aromatic amines enhanced the rate of reaction of higher yields of the products were obtained. The reactions were carried out at room temperature. Based on these observations, a mechanism for the oxidation of aromatic primary amines in presence of Ag(I) is proposed.