We report a robust pillar-layered metal-organic framework, Zn-tfbdc-dabco (tfbdc: tetrafluoroterephthalate, dabco: 1, 4-diazabicyclo[2.2.2]octane), featuring the fluorinated pore environment, for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture. The inverse propane-selective performance of Zn-tfbdc-dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms, isosteric enthalpy of adsorption calculations, ideal adsorbed solution theory calculations, along with the breakthrough experiment. The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane, as unveiled by the simulation studies at the molecular level. With the advantage of inverse propane-selective adsorption behavior, high adsorption capacity, good cycling stability, and low isosteric enthalpy of adsorption, Zn-tfbdc-dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.