In recent years, ynamides chemistry has emerged as a field of interest for the development of new synthetic methodologies. Here, we report a tandem azidination-[3 + 2] cycloaddition of ynamides to synthesize chiral ynamide substituted triazoles, which will be potentially useful in both material chemistry and medicinal chemistry. Vinyl or aryl azides were in situ generated through a Cu(I)-L-proline coupling of vinyl or aryl iodides with sodium azide, then terminal ynamides in DMSO solution were added by syringe pump to the system to initiate a Cu(I)-catalyzed ligation reaction of organic azides (without separation) and terminal ynamides; triazoles adduct were achieved in good to excellent yields. A competing azidination-[3 + 2] cycloaddition reaction between terminal ynamides and terminal alkynes was also studied.