Anilines are potentially high‐value arylating agents, but are limited by the low reactivity of the strong C‐N bond. We show that the reactive intermediate benzyne can be used to both activate anilines, and set‐up an aryl transfer reaction in a single step. The reaction does not require any transition metal catalysis or stoichiometric organometallics, and establishes a metal‐free route to valuable biaryl products by functionalizing the aniline C‐N bond.