Herein, we report the synthesis of zeolite composites with core-shell structure via a secondary growth technique and evaluation of their catalytic performance in ethanol dehydration. In particular, SAPO-34 particles were functionalized by TPA+, followed by dispersion in ZMS-5 or silicalite-1 to form SAPO-34@ZSM-5 and SAPO-34@silicalite-1 core-shell materials showed a hierarchical porous structure consisting of both micropores and mesopores. The active sites in the developed composites were found to have a mild acidity. Compared to conventional zeolite catalysts in ethanol dehydration reaction, the silicalite-1 composites. The novel core-shell materials showed a hierarchical porous structure consisting of both micropores and mesopores. The active sites in the developed composites were found to have a mild acidity. Compared to conventional zeolite catalysts in ethanol dehydration reaction, the core-shell SAPO-34@ZSM-5 improved the selectivity toward light olefins. In addition, our catalyst test results revealed the enhancement in propylene and ethylene yield over SAPO-34@ZSM-5 and SAPO-34@siliclite-1, respectively, as compared to that of bare SAPO-34. An improved catalyst stability was also obtained for the composite materials owing to their core-shell structure. The improved catalytic performance reported in this study reveals the potential utility of the zeolite composites with core-shell structure in ethanol dehydration reaction.