The growing demand for lithium necessitates sustainable extraction technologies that overcome the high energy consumption and geographical constraints of traditional evaporation and chemical precipitation. Here, we report the first mangrove-inspired photothermal–electrodialysis (PT–ED) system that achieves self-sustained, selective, and direct lithium salt extraction using only solar energy. The system integrates photo–electro–thermal (PET) coupling, where sunlight-driven photothermal evaporation and internally generated electric fields synergistically regulate ion migration and water removal within a single continuous process. This coordinated field interaction enables directional Li⁺ transport and controlled crystallization while preventing membrane fouling and parasitic salt deposition. Structural optimization of the leaf-shaped PT interface and an Li0.33La0.56TiO3 (LLTO)-based Li+-selective membrane ensures sustained operation and high selectivity. The PT–ED system delivers a Li+ flux of 9.6 mg m-2 h-1 and Li+/Mg2+ selectivity above 800, maintaining stable performance over 72 h and across brines collected from different salt lakes. This bioinspired PET approach offers a scalable pathway toward solar-driven, off-grid lithium recovery, establishing a universal framework for sustainable ion extraction, solar desalination, and circular water–energy utilization.