The imperative for efficient co-removal of arsenic (As) and fluoride (F^-) motivated the strategic immobilization of lanthanum (La) species onto {201}-faceted TiO₂ – a material exhibiting exceptional affinity toward arsenic species. Among three synthesis routes evaluated (incipient wetness impregnation, one-step solvothermal, and two-step hydrothermal methods), the two-step hydrothermal approach demonstrated superior fluoride sequestration performance. Subsequent optimization of synthesis pH and calcination temperature ( pH = 7 .5, 300^oC) further enhanced F^- removal efficacy. Nevertheless, the significant disparity in ionic radii between La³⁺ (1.032 Å) and Ti⁴⁺ (0.605 Å) inhibits direct substitution within O–Ti–O bonds, limiting the formation of stable O–La–O configurations and consequently constraining fluoride uptake capacity. This study provides a foundational framework for fabricating multifunctional bimetallic oxides incorporating high-index facets for complex water remediation scenarios.