Photocatalytic covalent organic frameworks (COFs) are ideal for uranium(VI) extraction, offering solutions for nuclear resource recovery and environmental remediation. This review evaluates design strategies for efficient U(VI) extraction, including donor–acceptor structure regulation, covalent linkage engineering, heterojunction construction, metal-COFs development, and piezophotocatalytic synergy. The mechanisms of photocatalytic U(VI) separation by COFs are also discussed.

The development of efficient and selective U(VI) extraction from seawater and U(VI)-containing wastewater through photocatalytic technology holds significant importance for nuclear energy advancement and mitigation of radionuclide-related environmental and health risks. Covalent organic frameworks (COFs) have emerged as ideal photocatalytic materials for U(VI) separation due to their inherent porosity, robust frameworks, chemical stability, and exceptional structural regularity. This comprehensive review examines molecular-level structural optimization of COFs to enhance charge carrier separation and transfer, thereby improving photocatalytic U(VI) extraction efficiency. Multiple design strategies are systematically evaluated, including donor–acceptor (D-A) structure regulation, covalent linkage engineering, COF-based heterojunction construction, metal–covalent organic frameworks development, and piezophotocatalytic synergy. Furthermore, the fundamental principles of U(VI) separation mediated by COFs are discussed and the mechanisms of U(VI) separation through photocatalysis by COFs are carefully analyzed. Finally, the challenges faced in the photocatalytic separation of U(VI) based on COFs are analyzed and their development prospects are searched. This review systematically summarizes the latest progress in the field of photocatalytic separation of U(VI) based on COFs, as well as the deficiencies in the catalytic mechanism. It can provide useful references for the rational design of efficient COF-based photocatalysts and in-depth exploration of the U(VI) separation mechanisms.