A series of phosphinimine ligands were designed and used in the Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of tetrazolo[1,5-a]pyridines and alkynes for the first time. By optimizing the reaction conditions, an efficient catalytic system (CuCl/2-PyCH2N[double bond, length as m-dash]P(t)Bu3) was developed to give 1-(pyridin-2-yl)-1,2,3-triazole derivatives in moderate to excellent yields (46-98%).