Tris(hydroxymethyl)aminomethane (THAM) is a highly efficient and recyclable organobase catalyst for the nucleophilic phosphonylation of benzylidene malononitrile under solvent-free conditions. This new catalytic methodology is applicable without a solvent, eco-friendly, economically viable, avoids conventional isolation procedures, and has a facile work-up procedure and wide scope. THAM is an inexpensive, commercially available, non-toxic, and biodegradable novel organocatalyst. Furthermore, it can be reused in up to five cycles without loss in catalytic activity, and no chromatographic separation is needed to obtain the desired products.