Efficient hydrogenation catalyst designing via preferential adsorption sites construction towards active copper

•In-situ reaction to form a stable macromolecule modified Cu catalyst.•The selective adsorption-desorption surface is main reason for the excellent catalytic performance.•CuAlOx-M affords desired products in up to > 99% yield with > 99% selectivity.•The method tolerates various unsaturated functional groups.•Provide a insight in precise constructing the catalytic active sites on heterogeneous catalyst.