: We report on a direct correlation between macroscale structural variations and the gas sorption capacities of an ion gel. Here, we chose 1-ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide ([Emim][TF2N]) and poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) as the ionic liquid and host polymer, respectively. The CO2 sorption in the thin films of IL-polymer was measured by the gravimetric method. The results of our experiment show that the trend of CO2 uptake of these mixtures is non-linearly correlated with the content of IL. Here we highlight the variation in the molecular structure of the polymers is the main reason behind the observed trend. The presented data suggest the possibility of using the composition of mixtures containing IL and polymers to realize a synergistic gain for gas sorption in these mixtures.