A highly efficient protocol has been developed for the three-component reaction of an amine, an aldehyde, and diethyl phopshite catalyzed by ZrOCl28H2O, an environmentally friendly catalyst, at ambient temperature. The catalyst exhibited remarkable activity and tolerated a wide variety of functional groups, providing the desired amino phosphonates in excellent yields under solvent-free conditions. Alternatively, the reaction rate can be significantly enhanced by carrying out the reaction in a monomode microwave reactor as a promoter.