A facile and versatile synthesis of ynamines via C(sp)-N bond formation was established. We installed an electron-withdrawing phosphoryl group onto the ynamines to isolate them by column chromatography. Phosphoryl ynamines were synthesized by treatment of bromo(phosphoryl)ethyne with diarylamine in the presence of K3PO4. Single-crystal X-ray analysis indicated double-bond characters of N-C, C=C, and C-P bonds in the N-C=C-P moiety. Phosphoryl ynamines could be used as terminal ynamine precursors in dephosphorylation/copper-catalyzed click reaction to form the corresponding 4-amino-1,2,3-triazoles in moderate yields.