AbstractFurfural was mainly used to produce furfuryl alcohol, which is a monomer of furan resins with a global market of ~$0.3 billion/year. Industrial production of furfuryl alcohol is via selective hydrogenation over toxic copper chromate under harsh conditions. Therefore, the search for active and non‐toxic alternatives is highly desired. Here, kinetics studies revealed an inhibitive effect caused by strong furfural adsorption on Ni‐based catalysts, resulting in sites blocking and undesired ring hydrogenation. Such an inhibitive effect can be alleviated over Ni‐Ga intermetallic surfaces by tuning the Ni coordination number, from which the Ni1Ga1 showed markedly enhanced furfuryl alcohol yield (~99%) at milder conditions comparing to the referred Ni catalyst. It is found that isolated Ni sites by Ga on the Ni1Ga1 enabled a tilted adsorption configuration through the carbonyl of furfural. In contrast, the stronger flat‐lying adsorption of furfural was favored on the contiguous Ni sites of the referred catalyst.