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α-Aminophosphonates possess a broad range of applications ranging from agrochemistry to medicine. We developed an efficient and eco-friendly Cellulose-SO3H catalyzed one-pot synthesis of α-aminophosphonates by three-component, room temperature reaction of an aldehyde, an amine and dialkylphosphite under solvent-free conditions. The major advantages of the present method are simple experimentation, use of inexpensive and eco-friendly reusable catalyst with good yields and short reaction times.