High fluoride concentrations in groundwater, especially in arid regions, is a widespread issue, posing severe threats to human health. Flow electrode capacitive deionization (FCDI) has emerged as a promising technology for treating fluoride-contaminated groundwater, but its practical application is constrained by limited Fselectivity, sluggish adsorption kinetics, and poor long-term stability. This study presents a Ce-doped NiCo layered double hydroxide (Ce-NiCo-LDH) as a tailored intercalation pseudocapacitive electrode material designed to enhance Fcapture performance. The Ce doping strategy induced the structural perturbations that generated abundant oxygen vacancies (Vo) and modulated the electronic structure via hybridized Ce4f/Ni3d valence bands. These modifications significantly enhance electron delocalization, reduce charge transfer resistance and promote pseudocapacitive behavior, enabling rapid, surface-controlled Fadsorption/desorption. As a result, the Ce-NiCo-LDH electrode achieves an average Fadsorption rate (AFAR) of 8.19 mg center dot m-2 center dot s-1, a fluoride adsorption capacity (FAC) of 56.23 mg center dot g-1. Critically, the system demonstrated robust efficacy in treating natural groundwater, reducing fluoride to below 1.0 mg center dot L-1. After 50 cycles, the electrode maintained 90.7% capacity, with comprehensive post-operation characterizations confirming its exceptional structural and chemical stability. Furthermore, the electrode demonstrates superior Fselectivity in competitive ionic environments (coexisting anions: NO3-, Cl-, SO42-), effectively overcoming the anion interference issue of undoped LDHs. Mechanistically, Ce doping creates Ce-Vo composite sites that function as strong Lewis acid centers and guided by the hard-soft acid-base (HSAB) theory, these sites exhibit inherent thermodynamic preference for F. Economic evaluation indicates a low specific energy consumption of 0.95 Wh center dot g-1 and an estimated treatment cost of $0.08-0.15 per m3, confirming its feasibility for large-scale engineering applications. Overall, this work provides new insights into the rational design of vacancy-engineered materials and significantly advances the engineering relevance of FCDI technology in addressing global fluoride pollution.