The metal-catalyzed nucleophilic aromatic substitution of hydrogen (SNArH) via coordination of the substituent on the aromatic ring to the metal catalyst, in terms of reactivity, substrate type, and reaction selectivity, complements the transition metal-catalyzed C-H functionalization that proceeds via C-H metalation but remains an elusive target. Described herein is the development of an unprecedented cobalt-catalyzed para-selective amination of azobenzenes, which is essentially a metal-promoted SNArH process as revealed by Hammett analysis, thus illustrating the concept that coordination of the substituent on the arene ring to the metal catalyst may result in electrophilic activation of the arene ring toward SNArH. This cobalt-catalyzed protocol allows the use of a variety of both aliphatic amines and anilines as aminating reagents, tolerates electronically diverse substituents of azobenzene, and furnishes the corresponding products in good yields with a regiospecific selectivity for para-amination.