Hydrogels　have　received　great　attention　due　to　their　molecular　designability　and　wide　application　range.　However,　they　are　prone　to　freeze　at　low　temperatures　due　to　the　existence　of　mass　water　molecules,　which　can　damage　their　flexibility　and　transparency,　greatly　limiting　their　use　in　cold　environments.　Although　adding　cryoprotectants　can　reduce　the　freezing　point　of　hydrogels,　it　may　also　deteriorate　the　mechanical　properties　and　face　the　risk　of　cryoprotectant　leakage.　Herein,　the　microphase-separated　structures　of　hydrogels　are　regulated　to　confine　water　molecules　in　sub-6 nm　nanochannels　and　increase　the　proportion　of　bound　water,　endowing　the　hydrogels　with　intrinsic　anti-freezing　properties,　high　mechanical　strength,　good　stretchability,　remarkable　fracture　energy,　and　puncture　resistance.　Even　after　being　kept　in　liquid　nitrogen　for　1000 h,　the　hydrogel　still　maintains　good　transparency.　The　hydrogel　can　exhibit　excellent　low-temperature　shape　memory　and　intelligent　optical　waveguide　properties.　Additionally,　the　hydrogel　can　be　assembled　into　strain　and　pressure　sensors　for　flexible　sensing　at　both　room　and　low　temperatures.　The　intrinsically　anti-freezing　microphase-separated　hydrogel　offers　broad　prospects　in　low-temperature　electronic　and　optical　applications.　©　2025　Wiley-VCH　GmbH.