Lithium mining is energy intensive and environmentally costly. This is because lithium ions are typically present in brines as a minor component mixed with physiochemically similar cations that are difficult to separate. Inspired by nature’s ability to selectively extract species in transpiration, we report a solar transpiration–powered lithium extraction and storage (STLES) device that can extract and store lithium from brines using natural sunlight. Specifically, the device uses a hierarchically structured solar transpirational evaporator to create a pressure gradient, which allows for the extraction of lithium from brines through a membrane and its storage in a vascular storage layer. Long-term experiments, various membrane tests, and different size assessments demonstrate the stability, compatibility, and scalability of STLES. This solar-powered mining technology provides an alternative developing pathway toward the sustainable extraction of critical resources.