Although metal-organic frameworks (MOFs) have been reported as important porous materials for the potential utility in metal ion separation, coordinating the functionality, structure, and component of MOFs remains a great challenge. Herein, a series of anionic rare earth MOFs (RE-MOFs) were synthesized via a solvothermal template reaction and for the first time explored for uranium(VI) capture from an acidic medium. The unusually high extraction capacity of UO₂²⁺ (e.g., 538 mg U per g of Y-MOF) was achieved through ion-exchange with the concomitant release of Me₂NH₂⁺, during which the uranium(VI) extraction in the series of isostructural RE-MOFs was found to be highly sensitive to the ionic radii of the metal nodes. That is, the uranium(VI) adsorption capacities continuously increased as the ionic radii decreased. In-depth mechanism insight was obtained from molecular dynamics simulations, suggesting that both the accessible pore volume of the MOFs and hydrogen-bonding interactions contribute to the strong periodic tendency of uranium(VI) extraction.