Chemodivergent (de)hydrogenative coupling of azoarenes with benzyl alcohols is achieved via the N=N bond activation using an inexpensive and well-defined (6-OH-bpy)NiCl2 catalyst. This protocol highlights the construction of C-N bonds via a borrowing hydrogen strategy that offers substituted imines and amines. A range of azo compounds couple with various substituted benzyl alcohols in a tandem hydrogenation/dehydrogenation process. The nickel catalyst along with the K2CO3 or (KOBu)-Bu-t base governed the selectivity in imine and amine formation. A preliminary mechanistic study establishes the crucial role of metal-ligand cooperation (MLC) comprising the distinct radical pathways.