Abstract This article discusses about the copper‐catalyzed electrophilic amination of heteroaromatic and aromatic C–H Bonds via TMPZnCl•LiCl mediated metalation.The importance of nitrogen‐containing compounds continues to drive the development of new C–N bond‐forming transformations. C–H amination offers a direct method to introduce amino groups into molecules without stepwise functional group manipulations. Organozinc reagents can be generated in situ using the strong and non‐nucleophilic base TMPZnCl•LiCl. Additionally, readily available O ‐benzoylhydroxylamines is demonstrated as an effective electrophilic nitrogen source in this C–H amination reaction.