We present here a novel fabrication of highly effective supported Pd catalysts (Pd@S-1@IL) derived fromPd@S-1 core–shell material coated with ionic liquids (ILs), [Prmim][Cl], for the selective hydrogenation ofacetylene. Catalytic testing on Pd@S-1@IL catalyst illustrated a remarkable selectivity towards semihydrogenation(over 90% for ethylene, irrespective of conversion level). Moreover, no indications ofdeactivation were observed after 800 h on stream even under relatively severe conditions. Detailedcharacterization indicated that the selectivity enhancement was ascribed to thefilter effect along withelectronic effect on the adsorption/desorption processes arising from the ionic liquids layer. The stability,which has ranked the top reported values over advanced Pd-based catalysts, is attributed to theconfinement effect of Pd NPs within the supports thus restricting the migration of metals. The fabricationof core–shell architecture combined with the advantages of ionic liquid layer offers a promising guidelinefor efficient catalytic transfer of chemical resource.