An efficient method for the synthesis of indole derivatives from readily available pyrimidyl‐substituted anilines and diazo compounds via rhodium(III)‐catalyzed C H bond activation has been developed. This cyclization reaction displays excellent functional group compatibility and regioselectivity, which overcomes some drawbacks of the classical indole synthetic methods and provides a facile approach for the construction of multi‐substituted indole derivatives. The redox‐neutral intermolecular annulation procedure comprises tandem C H bond activation, cyclization, and condensation steps, releasing water and nitrogen as by‐products.