Environmental concern associated with excess fluoride has intrigued the unceasing exploration of new multifunctional hybrid materials to mitigate any undesirable consequence to human health. Herein, a novel hybrid monolith has been successfully fabricated via a facile in-situ growth strategy for highly efficient defluoridation from contaminated waters, in which homogeneously dispersed UiO-66 particles are perfectly anchored on three dimensional (3D) porous carbon foam (CF). Benefiting from fully exposed active sites, excellent pore accessibility and efficient mass transport, the integrated UiO-66/CF hybrid monolith exhibits fast adsorption kinetics, and outstanding uptake capacity toward fluoride as high as 295 mg g−1, which greatly outperforms the previously reported adsorbents. Furthermore, the fluoride removal efficiency of the spent monolith can reach up to 70% after four cycles, accompanied by facile separation nature and outstanding water stability. More significantly, the resulting UiO-66/CF packed column (0.36 g) can continuously treat 400 mL of F− solution with 6.2 mg L−1 before the breakthrough point occurs, highlight its potential feasibility for fluoride removal in the practical applicability.