AbstractA novel and high efficient protocol was disclosed herein for the rare‐earth metal salt‐catalyzed substitution of phosphoryl azides with amines. In this homogeneous catalysis system, different diarylphosphoryl azides and aliphatic and aromatic amines were evaluated under the optimized reaction conditions, and a series of phosphoryl amides were generated through LaCl3 catalysis for the first time in moderate to excellent isolated yields. Different from well‐tolerated phosphoryl azide substrates, the amino nucleophiles, however, were mainly limited to primary amines; their secondary analogues or anilines were reluctant to experience desired transformations. Nevertheless, this methodology has proven to be a simple, practical, and scalable application of the promising lanthanide catalyst toward the exiting methodology library to prepare phosphoryl amides.