The request for both high catalytic selectivity and high catalytic activity is rather challenging, particularly for catalysis systems with the primary and side reactions having comparable energy barriers. Here in this study, we simultaneously optimized the selectivity and activity for acetylene semi-hydrogenation by rationally and continuously varying the doping ratio of Zn atoms on the surface of Pd particles in Pd/ZnO catalysts. In the reaction temperature range of 40-200 °C, the conversion of acetylene was close to ∼100%, and the selectivity for ethylene exceeded 90% (the highest ethylene selectivity, ∼98%). Experimental characterization and density functional theory calculations revealed that the Zn promoter could alter the catalyst's potential energy surface, resulting in a "confinement" effect, which effectively improves the selectivity yet without significantly impairing the catalytic activity. The mismatched impacts on activity and selectivity resulting from continuous and controllable alteration in the catalyst structure provide a promising parameter space within which the two aspects could both be optimized.