A S-scheme 2D/0D C₃N₅/Fe₂O₃ heterojunction photocatalyst was developed for enhanced uranium recovery from spent fuel reprocessing wastewater. The catalyst was designed based on built-in electric fields and energy band bending theory, enabling efficient photoreduction of hexavalent uranium (U(VI)) to tetravalent uranium (U(IV)), which is relatively insoluble and immobilized. The catalyst demonstrated high removal and recovery efficiencies of U(VI), achieving 93.38% and 83.58% removal and recovery rates, respectively, within 90 minutes. The heterojunction exhibited excellent catalytic activity and selectivity even in the presence of high concentrations of impurity cations and various organic compounds. The S-scheme configuration facilitated efficient electron transfer and reduced carrier recombination, enhancing the photocatalytic performance. The catalyst was also effective under simulated visible light conditions and showed stability after multiple regeneration cycles. The study highlights the potential of S-scheme heterojunctions for uranium recovery from nuclear wastewater, offering a promising solution for environmental remediation and resource recovery.A S-scheme 2D/0D C₃N₅/Fe₂O₃ heterojunction photocatalyst was developed for enhanced uranium recovery from spent fuel reprocessing wastewater. The catalyst was designed based on built-in electric fields and energy band bending theory, enabling efficient photoreduction of hexavalent uranium (U(VI)) to tetravalent uranium (U(IV)), which is relatively insoluble and immobilized. The catalyst demonstrated high removal and recovery efficiencies of U(VI), achieving 93.38% and 83.58% removal and recovery rates, respectively, within 90 minutes. The heterojunction exhibited excellent catalytic activity and selectivity even in the presence of high concentrations of impurity cations and various organic compounds. The S-scheme configuration facilitated efficient electron transfer and reduced carrier recombination, enhancing the photocatalytic performance. The catalyst was also effective under simulated visible light conditions and showed stability after multiple regeneration cycles. The study highlights the potential of S-scheme heterojunctions for uranium recovery from nuclear wastewater, offering a promising solution for environmental remediation and resource recovery.