<p>Efficient extraction of uranyl [U(VI)O₂²⁺] from fluoride-containing wastewater is important for both uranium mining and fuel rod manufacturing. However, it remains challenging due to the strong interaction between U(VI)O₂²⁺ and F⁻, which results in the formation of water-soluble and stable [UO₂F_<i>n</i>]^2−<i>n</i> (<i>n</i> = 0, 1, 2, 3, 4) complexes. Herein, we propose an innovative nanospace-confined adsorption electrocatalytic strategy (NAES) that enables efficient extraction of U(VI)O₂²⁺ from fluoride-containing wastewater. This is realized by rationally introducing amidoxime groups (R) into the interlayer region of a cobalt layered double hydroxide electrocatalyst (creating Co-LDH-R). The amidoxime groups selectively bind U(VI)O₂²⁺, which is further electrocatalytically converted to a K₅(UO₂)₂F₉ solid by the action of the Co²⁺ sites of Co-LDH-R through an electrocatalytic redox process in the presence of K⁺ and F⁻. Co-LDH-R can stably extract U(VI)O₂²⁺ from fluoride-containing wastewater streams, with a remarkable capacity of 7255.15 mg/g after 72 h, positioning it as one of the most effective U(VI) extractants reported to date. The generated solid K₅(UO₂)₂F₉ can be collected for storage or further processing. Therefore, our work offers a promising new pathway for uranium resource recovery under practical conditions.</p>