Treatment of salicylaldiminato ligand L1H−L2H (L1H = 2,4-di-tert-butyl-6-((quinolin-8-ylimino)methyl)phenol; L2H = 2,4-di-tert-butyl-6-(((2-(diethylamino)ethyl)imino)methyl)phenol) with Ni(OAc) 2 •4H 2 O in refluxing ethanol afforded nickel complexes [(L1)Ni(OAc)] (1) and [(L2)Ni-(OAc)] (2), respectively. Reaction of L3H (L3H = (2,4-di-tertbutyl-6-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenol)) with Ni-(OAc) 2 •4H 2 O in the presence of excess triethylanmine gave the dual ligands coordinated nickel complex [(L2) 2 Ni] ( 3). Complexes 1−3 were well characterized by high-resolution mass spectrometry, infrared spectroscopy, elemental analysis, and X-ray diffraction analysis. All the three Ni(II) complexes exhibited efficient activity and good selectivity in the acceptorless dehydrogenative coupling of alcohols and amines to produce imines and diimines. The present protocol provides an atom-economical and sustainable route for the synthesis of various imine derivatives by employing an earth-abundant nickel salt and easily prepared salicylaldiminato ligands.