In summary, we demonstrated the application of a PEC method to extract U from both synthetic U-containing water and mine tailings seepage water. The proposed PEC method can overcome the intrinsic drawbacks of the current photochemical methods by applying a bias potential on the photocatalyst, which drives spatial charge-carriers separation and decouples the U deposition sites and the photocatalyst active sites. As a result, the PEC method enables much faster U extraction and exceptional stability for both synthetic U-containing water and real U mine tailings seepage water. The economic analysis reveals that the proposed PEC U extraction method is an economically feasible approach. For the first time stable U(V) from aqueous media under ambient conditions was produced, implying the potential of the PEC method for the facile synthesis of U(V), which would facilitate future studies on U(V) chemistry.