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A simple and efficient method has been developed for the synthesis of α-aminophosphonates by a one-pot three-component condensation of aldehydes, amines and diethyl phosphite in the presence of a catalytic amount of silica sulfuric acid under solvent-free reaction conditions. The major advantages of the present method are good yields, inexpensive, ecofriendly and reusable catalyst, short reaction times, mild and solvent-free reaction conditions.