In this work, we fabricated a new type of Pd/SiO2@ZIF-8 core-shell catalyst composed of a Pd/SiO2 microsphere as the core and a ZIF-8 membrane as the shell. The preparation procedure involves first loading Pd nanoparticles onto nonporous SiO2 microspheres to obtain the Pd/SiO2 core and then coating a perfect layer of ZIF-8 shell on the core by electrostatic induction to form a Pd/SiO2@ZIF-8 core-shell structure. It is crucial that the modification of the Pd/SiO2 core with polyelectrolyte was employed to improve the charge distribution of the core surface and preferably adsorb Zn2+ cations in the synthesis solution so as to assist the formation of a continuous ZIF-8 shell. The compactness and thickness of the shell were optimized by increasing the number of cycles of ZIF-8 growth. The hydrogenations of alkenes with different molecular sizes showed that the Pd/SiO2@ZIF-8 catalysts can provide excellent product selectivity and antipoisoning and antileaching properties for the hydrogenations of alkenes.