The selective synthesis of different products from a substrate employing a single catalyst by altering the reaction conditions is challenging. Herein, easy-to-synthesize and cheap CuO NPs catalyzed chemodivergent transfer hydrogenation (TH) of azoarenes to hydrazoarene and aniline derivatives using ammonia borane (AB) under mild condition is disclosed. The practical applicability of the protocol was demonstrated by gram-scale synthesis of hydrazo and aniline derivatives as well as by the reduction of few commercially used dyes such as methyl red, sudan I, sudan III and solvent yellow 7. Several control experiment and deuterium labelling experiments were performed to understand the reaction mechanism. Moreover, the catalyst can be recycled up to six times without considerable loss of catalytic activity.