Excited-state nickel-catalyzed C-N cross-coupling of aryl bromides with sodium azide enables the synthesis of diarylamines and primary anilines under mild reaction conditions. The oxidative addition of electron-rich aryl bromides with low-valent Ni under the photochemical conditions is endothermic. Herein, we demonstrate a light-mediated nickel-catalyzed reaction of electronically rich aryl bromides that yields diarylamines, while the reaction with electron-deficient aryl bromides gives access to anilines at room temperature.