1-Amino-isoquinoline-N-oxides are generated under mild conditions through a tandem reaction of 2-alkynylbenzaldoxime with secondary amines in the presence of silver(I) and copper(I). The reaction proceeds smoothly at room temperature under air, leading to the corresponding products in good yields. During the reaction process, a silver-catalyzed 6-endo cyclization and a copper(I)-catalyzed C–H bond activation are involved.