We designed a core-shell zeolite structure comprises of palladium-deposited ZSM-5 core and silicalite-1 (S-1) shell which favors selectivity towards light olefin in hydrogenation via increased diffusion length. A well designed S-1/Pd/ZSM-5 core-shell structure was prepared via secondary crystallization of S-1 layer on the Pd/ZSM-5 core. The catalytic and selectivity performance of the S-1/Pd/ZSM-5 composite was evaluated in catalytic hydrogenation of alkenes in liquid phase. The synthesized S-1/Pd/ZSM-5 gives a much higher selectivity towards 1-hexene (87%) over cyclohexene (13%) even though both reactants are able to enter the 10-membered ring channels of the core-shell structure. The zeolitic core-shell composite also showed an increasing selectivity towards 1-hexene over 1-heptene as the S-1 layers built up, even though both are linear alkenes with similar kinetic diameter that are accessible to the MFI framework. In this work, we demonstrate a strong correlation between the thickness of the S-1 shell layer and the selectivity towards light olefins due to faster mass transfer rate. The design of the core-shell MFI structure is a new example of how selectivity in a zeolite-catalyzed reaction can be changed and enhanced without relying on typical molecular size exclusion process.