The photocatalytic conversion of soluble U(VI) into insoluble U(IV) is a robust strategy to harvest aqueous uranium, but remains challenging owing to the intermittent availability of solar influx and reoxidation of U(IV) without illumination. Herein, a dual platform based on K + and cyano group co-decorated poly(heptazine imide) (K-CN-PHI) is reported that can drive persistent U(VI) extraction upon/beyond light. K-CN-PHI achieves the photocatalytic reduction of U(VI) with a reaction rate of 0.89 min −1 , being 47 times greater than that over pristine carbon nitride (PCN). This system can further be triggered by light to form long-living radicals, driving the reduction of U(VI) in the dark for over 3 d. The flexible structural K + as counterions stabilize the electrons trapped by cyanamide groups, enabling the long lifetime of the generated radicals. The results collectively prove K-CN-PHI to be a novel and efficient photocatalyst enabling persistent U(VI) extraction around the clock, and broadening the practical applications of the photocatalytic extraction of U(VI).