A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH‐containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2‐picolylamine derivatives. The developed transformation was further utilized in a facile one‐pot synthesis of imidazo1,5‐apyridines. Insert here: A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH‐containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2‐picolylamine derivatives. The developed transformation was further utilized in a facile one‐pot synthesis of imidazo1,5‐apyridines. esp=α,α,α′,α′‐tetramethyl‐1,3‐benzenedipropionic acid, Ts=4‐toluenesulfonyl.