The nucleophilic aromatic substitution (S_NAr) reaction is a well-established protocol for synthesizing various biologically and synthetically relevant aromatic compounds.Among these methodologies, the vicarious nucleophilic substitution (VNS) is a powerful tool for achieving nucleophilic substitution at the sp² carbon bearing a hydrogen atom on (hetero)aromatics. Despite its significance in facilitating direct C–H functionalizations, the VNS reaction has intrinsic limitations, including lack of regioselectivity, limited substrate scope, and the need for prefunctionalized nucleophiles. We herein present a method for the vicarious-type nucleophilic amination of azine N-oxides and cyclic iminoamides using iminyl anions, readily generated from organic azides under basic conditions.