The selective synthesis of C-2/C-3 aminated five-membered heteroarenes incorporated various functionalities with aniline derivatives in a sustainable way remains an unmet challenge. This protocol presents a practical protocol for the C–H amination of heteroarenes via an electro-oxidative cross coupling process. This electrosynthetic approach enables a facile access to a wide variety of synthetically useful hetero-arene derivatives, tolerates a wide range of functional groups, and is amenable to gram scale synthesis. In addition, a preliminary mechanistic study reveals that a radical cross coupling process between the N-centered radical and indole radical cation may be involved for this amination reaction.