In existing CuAAC methods, the 1,4,5‐trisubstituted 1,2,3‐triazole unit usually was synthesized by trapping the 5‐metal‐1,2,3‐triazole intermediate (M=Cu, Bi or Al) with an electrophile. But, no 1,4,5‐trisubstituted 5‐dialkylamino‐1,2,3‐triazole has yet been synthesized for unknown reasons. We found that this problem may be caused by the strong oxidizing property of the amine electrophile (R2N+) or by the low reactivity of the MC bond in the intermediate. However, when a polymeric complex 1‐copper(I)‐alkyne was used as a substrate, the highly reactive 5‐copper(I)‐1,2,3‐triazole intermediate formed smoothly in the presence of the amine electrophile (R2N+). Finally, the first general synthesis of 1,4,5‐trisubstituted 5‐dialkylamino‐1,2,3‐triazoles was developed via the tandem reaction of 1‐copper(I)‐alkynes with azides and then with O‐benzoyl hydroxylamines at room temperature which occurred within five minutes.magnified image