A hierarchical zeolite was synthesized by self-assembly of ZSM-5 nano-crystals colloid and polystyrene spheres coated with cationic poly (diallyldimethylammonium chloride). The colloidial ZSM-5 nano-crystals were first bound onto the polyelectrolyte-modified PS by electrostatic attraction, followed by centrifugation to form PS/ZSM-5 close-packed composite. After being dried and calcined to remove the organic components, the hierarchical zeolite was obtained. The X-ray diffraction, scanning electron microscopy, transition electron microscopy and N2 adsorp-tion-desorption techniques were employed to characterize the hierarchical zeolite. The results showed that the material prepared by this method was well crystallized and possessed uniform ma-cropores interconnected in three dimensions through windows. Furthermore, the hierarchical zeolite was rather mechanically stable.