Recent advances in thermally localized solar evaporation hold significant promise for vapor generation, seawater desalination, wastewater treatment, and medical sterilization. However, salt accumulation is one of the key bottlenecks for reliable adoption. Here, we demonstrate highly efficient (>80% solar-to-vapor conversion efficiency) and salt rejecting (20 weight % salinity) solar evaporation by engineering the fluidic flow in a wick-free confined water layer. With mechanistic modeling and experimental characterization of salt transport, we show that natural convection can be triggered in the confined water. More notably, there exists a regime enabling simultaneous thermal localization and salt rejection, i.e., natural convection significantly accelerates salt rejection while inducing negligible additional heat loss. Furthermore, we show the broad applicability by integrating this confined water layer with a recently developed contactless solar evaporator and report an improved efficiency. This work elucidates the fundamentals of salt transport and offers a low-cost strategy for high-performance solar evaporation.