Here, we report a new approach for preparing zeolite-polymer core-shell-like materials with hierarchical porosity via photopolymerization of trifunctional acrylic monomer (TMPTA) under UV–visible irradiation using a bifunctional Silane-based Photoinitiator (SPI-1) as coupling agent. The free radicals generated on the surface of zeolites initiate the polymerization of the diluted monomers, creating an external and mesoporous polymer shell layer. The efficiency of the photopolymerization process and the textural properties of synthesized materials are investigated using different techniques, including PXRD, TGA, UV–Vis, FTIR, SEM, and TEM. The accessibility to the pores of the zeolite core is investigated by N2 physisorption at 77 K and other probe molecules using IR spectroscopy. Interestingly, the results demonstrate a good covering of the zeolite surfaces by polymers shell. The new approach is highly repetitive and reproducible, and the accessibility to the zeolite's micropores is preserved at around 90%, which is not reported previously. The hybrid materials show higher hydrophobicity and higher ethanol adsorption capacities compared to the parent material and are potential candidates for ethanol dehydration, demonstrating a new and easy way for preparing zeolite/polymer hybrid materials for various applications such as ethanol dehydration