Dehydrogenative C−H/N−H cross‐coupling serves as one of the most straightforward and atom‐economical approaches for C−N bond formation. In this work, an electrochemical reaction protocol has been developed for the oxidative C−H amination of unprotected phenols under undivided electrolytic conditions. Neither metal catalysts nor chemical oxidants are needed to facilitate the dehydrogenation process. A series of triarylamine derivatives could be obtained with good functional‐group tolerance. The electrolysis is scalable and can be performed at ambient conditions.