Triazene and trizole derivatives have biological and industrial activities. For instance N-substituted phosphorous benzotriazole derivatives are used for peptide synthesis. This study describes a simple, efficient and metal free method for synthesis of N-substituted derivatives of benzotriazoles and diphenyltriazenes containing phosphorous atom through a chemoselective process. The chemical structures of the new compounds were confirmed by elemental and spectral (1H NMR, 13C NMR and IR) analysis.