Carbon dioxide (CO₂) emissions intensify the greenhouse effect so much that its capture and separation are needed. Porous liquids, possessing both the porous properties of solids and the fluidity of liquids, exhibit a wide range of applications in absorbing CO₂, but the mechanism of gas capture and separation demands in-depth understanding. To this end, we provide a molecular perspective of gas absorption in a porous liquid composed of porous organic cages dissolved in a size-excluded solvent, hexachloropropene, by density functional theory for the first time. In this work, different conformations were considered comprehensively for three representative porous organic cages and molecules. Results show that chloroform, compared to CO₂, tends to enter the cage due to stronger C–H⋯π interaction and the optimal capacity of each cage to absorb CO₂ through hydrogen bonding and π–π interaction is 4, 2 and 4 equivalents, respectively. We hope that these discoveries will promote the synthesis of similar porous liquids that are used to capture and separate gases.