Copper(I)-catalyzed N-O bond formation reactions through vinyl nitrene-mediated pathway were described. The reactions of N-alkoxylbenzamides and 2 H-azirines afforded α-amino oxime ethers in good to excellent yields at room temperature, which involved the cleavage of C-N and N-O bonds and the construction of new N-O and C-N bonds. It offers an efficient, regio- and stereoselective synthetic route for α-amino oxime ethers.