A novel and simple approach to the multicomponent one-pot reaction of aldehydes, diethyl phosphite, and azides to form α-aminophosphonates under solvent-free conditions at room temperature has been developed. In the presence of iodine and iron, aryl azides were, for the first time, used as substrates for the synthesis of α-aminophosphonates. The reactions were completed within 5 minutes to 12 hours and afforded the corresponding products in good yields.