An unprecedented Rh-catalyzed direct addition of aryl C–H bonds to nitrosobenzenes has been developed under very mild reaction conditions (room temperature). The reaction is highly step-, atom-, and redox-economic and compatible with air and water to <i>N</i>-selectively provide a variety of <i>N</i>-diarylhydroxylamines in good to excellent yields. More importantly, this process may provide a new direction for C–N bond formation through direct C(sp<sup>2</sup>)–H functionalization
