AbstractHydrogel‐based solar evaporators (HSEs) emerged as energy‐efficient designs for water purification due to the reduced vaporization enthalpy in the hydrated polymeric network. However, it remains challenging for HSEs to achieve stable performance in desalination, partly due to the tradeoff between desired evaporation dynamics and salt tolerance. Here, composite hydrogels with tunable self‐assembled nanofiber networks are exploited for the engineering of solar evaporators with both high evaporation performance and resistance to salt accumulation. The nanofibrous hydrogel solar evaporators (NHSEs) present an intrinsic open network with high porosity, above 90%, enabling continuous water channels for efficient mass transfer. Theoretical modeling captures the complex nexus between microstructures and evaporation performance by coupling water transfer, thermal conduction, and vaporization enthalpy during evaporation. The mechanistic understanding and engineering tuning of the composites lead to an optimum configuration of NHSEs, which demonstrate a stable evaporation rate of 2.85 kg m−2 h−1 during continuous desalination in 20% brine. The outstanding performance of NHSEs and the underlying design principles may facilitate further development of practical desalination systems.