Here we show that the photoelectrochemical (PEC) method could effectively resolve the aforementioned drawbacks of PC methods, by applying a bias potential on the photocatalyst (Figure ). The PEC method enables much faster U extraction and exceptional stability for both synthetic U-containing water and real U mine tailings seepage water. We further show that the bias-driven spatial charge-carriers separation is the key to obtain fast U extraction and high stability. In synthetic U-bearing water, the PEC U extraction proceeds via single-step oneelectron reduction. For the first time we produced stable U(V) from aqueous media under ambient conditions without using organic ligands, implying the potential of the PEC method for facile U(V) synthesis, which would significantly facilitate future studies on U(V) chemistry.