The vicinal diamine motif plays a significant role in natural products, drug design, and organic synthesis, and development of synthetic methods for the synthesis of diamines is a long-standing interest. Herein, we report a regioselective intermolecular three-component vicinal diamination of styrenes with acetonitrile and azodicarboxylates. The diamination products can be produced in moderate to excellent yields via the Ritter reaction. Synthetic applications and theoretical studies of this reaction have been conducted.