<p>Electrochemical extraction of uranium from seawater is a promising strategy for the sustainable supply of nuclear fuel, whereas the current progress suffers from the co-deposition of impurities. Herein, we construct a synergistic coordination-reduction interface in CMOS@NSF, achieving electrochemical extraction of black UO₂ product from seawater. The internal sulfur of CoMoOS tailors the electron distribution, resulting in the electron accumulation of terminal O sites for strong uranyl binding. Meanwhile, the interfacial connection of CoMoOS with Ni₃S₂ accelerates the electron transfer and promoted the reductive properties. Such synergistic coordination-reduction interface ensures the formation and preservation of tetravalent uranium, preventing the co-deposition of alkalis in crystalline transformation. From natural seawater, CMOS@NSF exhibits an electrochemical extraction capacity of 2.65 mg g⁻¹ d⁻¹ with black UO₂ solid products as final products. This work provides an efficient strategy for the electrochemical uranium extraction from seawater with low impurities.</p>