<p>Selective extracting uranium from seawater is quite challenging, particularly the presence of vanadium, which poses a significant obstacle for most amidoxime absorbents. Adsorbents with size-matched pores and coordination environment can improve the uranium selectivity but usually deteriorate the adsorption capacity. Herein, a dynamically matched spatial coordination strategy is proposed to improve the performance of uranium extraction. The diarylethene (DAE) photoswitch with photoisomerization characteristic is introduced into Metal-Organic Frameworks (MOFs), in which the tunable pore size and coordination environment provide a precisely confined space for uranium capture under the dynamic adjustment of ultraviolet-visible (UV-Vis) irradiation. Proposed material with photo-responsive gated rectification capability can effectively extract uranium from vanadium-rich system, the uranium adsorption capacity reaches 588.24 mg·g⁻¹ and the U(VI)/V(V) separation factor ratio is recorded up to 215. Finite element simulation confirms the enhancement of mass transfer under the open-state of DAE, which leads to the improved adsorption capacity. Density Functional Theory (DFT) calculations suggest size-matching between pore structure and uranium species, as well as the spatial coordination between the closed-state DAE and uranium species, results in the U(VI)/V(V) selectivity and uranium extraction performance. Current work presents a promising strategy for improving the uranium extraction ability and U(VI)/V(V) selectivity under seawater environment.</p>