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 N-selectively provide a variety of N-diarylhydroxylamines in good to excellent yields. More importantly, this process may provide a new direction for C-N bond formation through direct C(sp(2))-H functionalization.