The　development　of　low-cost　nickel-based　catalysts　for　direct　and　selective　hydrogenation　of　2-butyne-1,4-diol　(BYD)　to　butane-1,4-diol　(BAD)　under　mild　conditions　is　an　important　and　attractive　target　both　in　fundamental　research　and　industrialization　but　remains　a　formidable　challenge.　The　primary　industrial　production　method　for　BAD　synthesis　is　a　two-step　reaction　route,　which　suffers　from　complicated　catalysis　conditions　and　high　equipment　costs.　Herein,　we　develop　a　high-performance　catalyst　via　a　facile　alcohol-treated　strategy　for　highly　selective　BAD　synthesis　at　moderate　operation　conditions.　The　as-synthesized　NA-80E　catalyst　exhibits　outstanding　BAD　selectivity　of　98.82　%　and　BYD　conversion　of　100　%　at　60　°C　and　4　MPa,　outperforming　most　reported　results　for　BAD　formation　in　a　one-step　process　and　even　being　comparable　to　those　obtained　by　the　two-step　hydrogenation　reaction　route　under　much　high　temperatures　and　pressures.　Crucially,　we　found　that　after　facile　alcohol　(ethanol)　treatment,　an　intriguing　phenomenon　of　suppression　of　adjacent　acid-assisted　hydrogenolysis　via　extra　acidic　Al　species　at　the　NiO-Al2O3　interface　is　observed,　contributing　to　the　precise　enhancement　of　BAD　selectivity　by　inhibiting　the　production　of　butanol　(BOL).　This　facile　alcohol-treated　method　along　with　the　revealed　mechanism　of　blocked　hydrogenolysis　opens　vast　possibilities　for　designing　high-performance　and　highly-selective　hydrogenation　catalysts.　©　2023　Wiley-VCH　GmbH.