In this study, lamellar MFI (Mobile Five-membered ring Intergrowth) zeolites pillared with TiO₂ were synthesized using tetraethyl orthotitanate (TEOTi) as titanium precursor and evaluated as photocatalysts for Rhodamine B (RhB) degradation under UV irradiation. The materials were characterized by X-ray diffraction (XRD), UV–Vis spectroscopy, N₂ adsorption–desorption, photoluminescence spectroscopy (PL), and transmission electron microscopy (TEM). XRD confirmed the preservation of the lamellar MFI structure and the formation of anatase TiO₂ pillars within the interlayer space. The composites exhibited hierarchical micro/mesoporosity, high surface areas (>320 m² g⁻¹), and mesopore sizes of approximately 4.1–4.2 nm. Photocatalytic experiments revealed that the incorporation of TiO₂ into the lamellar MFI framework significantly enhanced the degradation kinetics of RhB compared with bare TiO₂. The apparent pseudo-first-order rate constants followed the order MFIPTi-6 > MFIPTi-3 > MFIPTi-12 > TiO₂ > MFIPTi-24, with MFIPTi-6 exhibiting the highest activity (k_app = 0.049 min⁻¹), approximately 1.6 times higher than that of pure TiO₂. Scavenger experiments identified hydroxyl radicals as the predominant reactive species involved in the degradation process. TOC (Total Organic Carbon) measurements showed approximately 80% organic carbon removal, while recyclability tests demonstrated stable photocatalytic performance over six consecutive cycles. These results highlight the potential of lamellar TiO₂/MFI composites as efficient and reusable photocatalysts for water treatment applications.