Nickel(II) complexes have been synthesized and characterized using nuclear magnetic resonance (NMR), infrared spectroscopy, high resolution mass spectroscopy, and elemental analysis. The complexes were evaluated as pre-catalysts in the direct hydrogenation of furfural to furfuryl alcohol. The pre-catalysts C1 and C4 gave higher furfural conversion (97% and 96%, respectively), as a result, they were also evaluated in the transfer hydrogenation of furfural using formic acid as the hydrogen source where higher furfural conversion (93%) was obtained and selectivity (100%) toward the formation of furfuryl alcohol at 4 h. The catalyst C1 was recycled three times with and it was observed that the catalytic activity might be due to a mixture of both molecular catalysis and nanoparticles, as evidenced by the decrease in activity in mercury poisoning experiments. The hydrogenation reactions were also extended to alpha-β unsaturated substrates and were selective toward saturation of the carbonyl functionality over alkene groups.