A new Pd@ZIF-L hybrid catalyst having a unique crosshair-star shape with a size of about 20 μm was synthesized, in which a two-dimensional layered zeolitic imidazolate framework-L (ZIF-L) was used as a support to immobilize palladium nanoparticles via an assembly method. The hybrid catalyst with unique cushion-shaped cavities between layers with a size of 6.64 Å can be used for the diffusion of specific reactants not achievable by other ZIF systems such as ZIF-8. The crystal structure and morphology of Pd@ZIF-L are strongly dependent on the synthesis conditions. Palladium nanoparticles with an average size of 3 nm are homogeneously encapsulated in the ZIF-L crystals. The as-synthesized Pd@ZIF-L catalyst favors the conversion of alkenes with larger molecular sizes, and exhibits excellent molecule-size-selectivity and anti-leaching performance.