The synthesis of chiral triazole-fused pyrazine scaffolds from readily available substrates in a step-economical asymmetric catalytic way is highly appealing. We herein report that an efficient Cu/Ag relay catalyzed protocol employing cascade asymmetric propargylic amination, hydroazidation, and [3 + 2] cycloaddition reaction with high efficiency to access the target enantioenriched 1,2,3-triazolo[1,5-a]pyrazine has been accomplished by applying a novel N,N,P-ligand. The one-pot reaction of three components exhibits high functional group tolerance, excellent enantioselectivities, and a broad substrate scope with readily available starting materials.