Interfacial solar vapor generation (SVG) is regarded as a promising and sustainable strategy for clean water production. While many materials have demonstrated excellent evaporation rates under one sun, it remains challenging to design solar evaporators without compromising SVG performance in high‐salinity brines (≥10 wt %). Herein, polyzwitterionic hydrogels (PZHs) are proposed as a novel platform for high‐salinity solar desalination. Taking advantage of the unique anti‐polyelectrolyte effects, PZHs can trap salt ions from the brine water to form a more hydrated polymer network, leading to enhanced SVG performance. PZHs exhibit an exceptional solar evaporation rate of 4.14 kg m−2 h−1 in 10 wt % brine, which is ≈20 % higher than that in pure water. It is anticipated that salt‐responsive PZHs may provide insights for the design of next‐generation solar desalination systems. A novel polyzwitterionic hydrogel as highly efficient solar evaporator is developed for high‐salinity solar desalination. The hydrogel evaporator could achieve a rapid solar evaporation rate of 4.14 kg m−2 h−1 with high energy efficiency (≈94 %) in 10 wt % brine. This polyzwitterionic hydrogel offers insight to design next‐generation solar evaporators for high‐salinity brine.