Supported NiO nanoclusters were prepared by using nickel colloid as a precursor. NiO nanoclusters wer supported on hydrotalcite and the obtained catalyst was applied to oxidative dehydrogenation of alcohols. As a consequence, the prepared catalyst showed the highest activity compared to conventional heterogeneous nickel-based catalysts under clean reaction condition such as molecular O-2 as an oxidant and base free conditions. Utilizing nanocluster and support facilitated the high activity for the reaction.