In this work, a CdS/BiVO 4 step-scheme (S-scheme) heterojunction with self-photothermally enhanced photocatalytic effect was synthesized and applied for efficient U(VI) photoextraction. Characterizations such as transient absorption spectroscopy and Tafel test together confirmed the formation of S-scheme heterojunctions, which allows CdS/BiVO 4 to avoid photocorrosion while retaining the strong reducing capacity of CdS and the oxidizing capacity of BiVO 4 . Experimental results such as radical quenching experiments and electron spin resonance show that U(VI) is rapidly oxidized by photoholes/ • OH to insoluble UO 2 (OH) 2 after being reduced to U(IV) by photoelectrons/ • O 2 - , which precisely avoids the depletion of electron sacrificial agents. The rapid recombination of electron-hole pairs triggered by the S-scheme heterojunction is found to release large amounts of heat and accelerate the photocatalysis. This work offers a new enhanced strategy for photocatalytic uranium extraction and presents a direction for the design and development of new photocatalysts.