The development of industrial catalysts is of crucial importance for practical uses. However, the use of extruded catalysts in industry is still limited because of a remarkably decreased catalytic activity when combining them with binders. This contribution illustrates the rational design of binder-free hierarchical ZSM-5 pellets and monoliths derived from zeolite@LDHs composites via extrusion and 3D printing technologies, respectively. The designed catalyst applied in bioethanol dehydration boosts the ethylene yield by over 93.4 ± 2.2% due to the synergistic effect of zeolites and LDHs.