The　separation　of　n-alkanes　from　their　branched　isomers　is　vitally　important　to　improve　octane　rating　of　gasoline.　To　facilitate　mass　transfer,　adsorptive　separation　is　usually　operated　under　high　temperatures　in　industry,　which　require　considerable　energy.　Herein,　we　present　a　kind　of　dynamic　pillar-layered　MOF　that　exhibits　self-adjustable　structure　and　pore　space,　a　behavior　induced　by　guest　molecules.　A　combination　of　the　flexibility　of　the　framework　with　the　commensurate　adsorption　for　n-hexane　results　in　exceptional　performance　in　separating　hexane　isomers.　More　significantly,　lower　temperature　prompts　the　guest　molecules　to　open　the　dynamic　pores,　which　may　provide　a　new　perspective　for　optimized　separation　performance　at　lower　temperatures　with　less　energy　consumption.