<p>Fluoride contamination represents one of the most pervasive and severe challenges in global aquatic environments, creating an imperative for the development of highly efficient F^- removal materials. Here, we design a core–shell composite comprising a ZSM-5 molecular-sieve core encapsulated within a lanthanum-intercalated layered double hydroxide (LDH) shell. The ZSM-5 microporous scaffold provides rigid structural support and long-range ion pathways, whereas La³⁺ doping expands the interlayer spacing and induces wrinkled LDH nanosheets, substantially increasing the surface area and mesoporosity (413 m²·g^-1; 0.931 cm³·g^-1) and generating highly reactive La–F coordination sites via enhanced M–O polarization. XPS, DFT, and MD results confirm La³⁺ as the strongest Lewis acidic center with the most negative adsorption energy, enabling rapid F^- capture and robust interfacial enrichment under NO₃^- and SO₄^2- backgrounds. Benefiting from the synergistic structural–electronic regulation, Z-NAL4 delivers a Langmuir capacity of 82.4 mg·g^-1 at 25&#xa0;°C and &gt; 99.9% defluoridation at only 0.50–0.60&#xa0;g·L^-1, while retaining 88.1% after five regeneration cycles. Granulated composites further extend the fixed-bed breakthrough time to 13.7&#xa0;h. This work establishes a unified “structure–electronics–transport” design framework that connects La³⁺-driven interfacial coordination chemistry with bio-inspired multiscale diffusion, providing a promising platform for treating complex fluoride-laden effluents in fluorochemical production and lithium-salt recovery.</p>