In　recent　years,　gel-electrolyte　becomes　pivotal　in　preventing　hydrogen　evolution,　reducing　dendrite　growth,　and　protecting　the　zinc　metal　anode　for　zinc-ion　batteries.　Herein,　a　polyvinyl　alcohol-based　water–organic　hybrid　gel　electrolyte　with　Agar　and　dimethyl　sulfoxide　is　designed　to　construct　the　spontaneous　desaturation　of　the　solvation　sheath　for　reducing　hydrogen　evolution　and　dendrite　growth　at　room　temperature　and　even　low　temperature.　According　to　experimental　characterization　and　theoretical　calculations,　the　well　binding　between　multihydroxy　polymer　and　H2O　is　achieved　in　the　hybrid　desaturated　gel-electrolyte　to　regulate　the　inner　and　outer　sheath.　The　ionic　conductivity　of　hybrid　gel-electrolyte　reaches　7.4　mS　cm−1　even　at　−20 °C　with　only　0.5 m　zinc　trifluoromethanesulfonate　(Zn(OTf)2).　The　Zn　symmetric　cells　cycle　over　1200 h　under　26　and　−20 °C　with　improved　mechanical　properties　and　electrochemical　performance.　The　asymmetric　Zn　||　Cu　cell　with　hybrid　gel　electrolyte　reaches　≈99.02%　efficiency　after　250　cycles.　The　capacity　of　full　cell　is　maintained　at　around　74　mAh　g−1　with　almost　unchanged　retention　rate　from　50　to　300　cycles　at　−20 °C.　This　work　provides　an　effective　strategy　for　desaturated　solvation　to　reach　anti-freezing　and　high-density　Zn　energy　storage　devices.　©　2023　Wiley-VCH　GmbH.