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-PyCH₂NP^tBu₃) was developed to give 1-(pyridin-2-yl)-1,2,3-triazole derivatives in moderate to excellent yields (46–98%).