Zinc-ion　hybrid　capacitors　(ZIHCs)　are　famous　for　potential　applications　in　grid-scale　energy　storage　devices　with　fast-charge　capability.　However,　their　industrialization　is　severely　plagued　by　inferior　performance　caused　by　the　sluggish　Zn2+　desolvation　kinetics　with　large　spatial　diffusion　hinderance　of　[Zn(H2O)6]2+　in　the　inner　Helmholtz　plane　(IHP)　layer,　especially　under　low-temperature　surroundings.　Herein,　the　simultaneous　rapid　desolvation　strategy　via　pore　sieving　and　electrocatalysis　is　initially　proposed　to　promote　[Zn(H2O)6]2+　dissociation,　regulating　the　isolated　Zn2+　behaviors　in　the　IHP.　Specifically,　heteroatom-decorated　carbon　microspheres　with　multi-level　channels　modulate　the　local　distribution　of　electronic　density,　generating　abundant　catalytic　sites　to　drive　the　kinetics　of　[Zn(H2O)6]2+　desolvation　and　free　Zn2+　diffusion.　Impressively,　the　catalytic　desolvation　behaviors　and　storage　mechanism　of　ZIHCs　are　comprehensively　investigated　using　in-situ　electrochemical　quartz　crystal　microbalance　and　various　ex-situ/in-situ　measurements　as　well　as　theoretical　simulations,　revealing　significant　interactions　of　isolated　Zn2+　in　the　IHP.　Consequently,　the　assembled　ZIHCs　exhibit　a　superior　capacity　of　177.2　mAh　g-　1,　corresponding　to　a　high　energy　density　of　158.8　Wh　kg-1,　and　provide　a　power　density　as　high　as　15.7　kW　kg-1.　Exposed　to　extreme　environment,　the　ZIHCs　encountered　with　severe　solvation　structure　stabilize　for　10000　cycles　withcapacity　retention　of　99.42%,　providing　new　insights　of　catalytically　sieving　into　modulating　IHP　for　high-performance　ZIHCs　under　extreme　conditions.