An efficient and convenient one-pot protocol is developed to prepare aryl/alkyl mixed phosphates in the presence of copper catalyst under exceptionally mild conditions. A series of versatile, ubiquitous, and inexpensive phosphoryl azides and aliphatic alcohols are combined for the first time ever. Diphenylphosphoryl azide is employed as novel phosphors reagent through an unexpected cleavage of P-N bond. The transformation is advantageous with respect to a broad of functional group compatibility and different esterification products are isolated in good to excellent results. This new catalytic system represents a superior platform towards a mild, operationally simple, practical, and scalability alternative to access target molecules. Furthermore, a plausible mechanism is proposed based on insightful mechanistic studies. (C) 2019 Elsevier Inc. All rights reserved.