Display omitted •A 3D rice-like hierarchical nanocomposite was designed by anchoring La species into LDH matrix.•La@MgAl achieved high adsorption capacities for both phosphate and fluoride.•Satisfactory selectivity and reusability of the adsorbent were proved.•Interlayer sorption and inner-sphere complexation were main mechanisms for excellent adsorption performance.•La@MgAl was effective for synchronous phosphate and fluoride remediation in real wastewater. The frequent occurrence of algae boom and skeletal fluorosis has drawn global attention to developing feasible technologies for phosphate and fluoride removal from water bodies. This study reported the synthesis of novel three-dimensional rice-like La@MgAl nanocomposites by anchoring La species into Mg-Al LDH matrix to achieve effective and synchronous phosphate and fluoride capture. Results from multiple detection methods including XRD, SEM, FTIR, and XPS revealed the introduced La cations could serve as a structural inducer to regulate the crystallinity of the La@MgAl composites and rice-like nanocomposite La@MgAl-1 was fabricated under optimal La loading amount. La@MgAl-1 possessed high adsorption capacities for both phosphate and fluoride (101.59 mg/g and 51.03 mg/g, respectively). The effective adsorption performance also sustained even after five adsorption-desorption cycles, indicating favorable reusability. The adsorption mechanism analysis revealed that the presence of unique hydrotalcite-like structure triggered memory effect to exert strong adsorption of P and F anions into the interlayered gallery. Besides, an optimum amount of La species organized on the composite wielded specific anion adsorption to phosphate and fluoride through inner-sphere complexation and ligand exchange. These encouraging results highlight the positive consequence of combining the strategic La species and LDH matrix to render a nanostructured Mg/Al/La ternary metal assembly in which various components are united in a controllable way to exert collective properties for accumulative anion adsorption properties. Besides, this study offered promising candidates for real water purification against phosphate and fluoride pollution.