Sufficient and clean freshwater is still out of reach for billions of people around the world. Solar desalination from brine is regarded as one of the most promising proposals to solve this severe crisis. However, most of the reported evaporators to date still suffer from the decreasing evaporation rate caused by salt crystallization accumulated on their surface. Here, inspired by the vascular tissue structure, transpiration, and antifouling function of reed leaves, we design biomimetic hierarchical nanofibrous aerogels with parallel-arranged vessels and hydrophobic surfaces for highly efficient and salt-resistant solar desalination. Foldable vessel walls and flexible silica nanofibers give the reed leaf-inspired nanofiber aerogels (R-NFAs) excellent mechanical properties and enable them to withstand repeated compression. Besides, the R-NFAs can efficiently absorb sunlight (light absorption efficiency: 94.8%) and evaporate the brine to vapor, similar to reed leaves (evaporation rate: 1.25 kg m −2 h −1 under 1 sun). More importantly, enabled by the hydrophobic surfaces and parallel-arranged vessels, the R-NFAs can work stably in high-concentration brine (saturated, 26.3 wt %) under high-intensity light (up to 6 sun), demonstrating potent salt resistance. It is expected that R-NFAs with combined antisalt pore and surface structures will provide a designed concept for salt-resistant solar desalination.