Developing　advanced　ion-conductive　networks　is　crucial　for　anion　exchange　membranes　(AEMs).　A　flexible　molecular　structure　facilitates　the　formation　of　ion　clusters,　resulting　in　enhanced　ionic　conductivity.　Polyacrylates,　known　for　their　outstanding　flexibility　and　chemical　stability,　hold　significant　potential　as　polymer　electrolyte　membranes.　In　this　work,　we　innovatively　constructed　a　series　of　polyacrylate-based　AEMs　decorated　with　pendant　zwitterions　(designated　as　PSBPA-X,　BSBPA-X,　where　X　=　20,　30,　40).　Specifically,　the　spacer　length　between　the　zwitterions　is　strategically　optimized　to　enhance　the　ionic　conductivity.　Atomic　force　microscopy　reveals　that　a　longer　spacer　length　between　the　zwitterions　promotes　the　microphase　separation　and　the　formation　of　advanced　water　channels,　which　facilitates　the　OH−　transport　in　the　BSBPA-40　membrane.　Moreover,　the　stronger　electrostatic　potential　and　lower　interaction　energy　between　the　BSBPA-40　and　OH−　further　contribute　to　efficient　OH−　hopping　transmission.　Consequently,　the　BSBPA-40　membrane　demonstrates　the　highest　OH−　conductivity,　achieving　102.1　mS　cm−1　at　80　°C　and　90%　relative　humidity,　significantly　surpassing　that　of　the　PSBPA-40　membrane　(75.2　mS　cm−1).　Additionally,　the　BSBPA-40　membrane　exhibits　remarkable　flexibility　with　an　improved　breaking　elongation　of　480.5%　due　to　the　ionic　cross-linking　between　the　zwitterions.　Notably,　the　BSBPA-40　membrane-based　zinc-air　battery　achieves　an　outstanding　power　density　of　156.7　mW　cm−2　at　room　temperature,　while　its　water　electrolysis　performance　reaches　2.1　A　cm−2　at　2.0　V.　These　results　indicate　that　the　developed　membranes　hold　great　promise　for　applications　in　sustainable　and　clean　energy　technologies.　©　2025　Institute　of　Process　Engineering,　Chinese　Academy　of　Sciences