The CO₂ sorption and polymer swelling of hydroxytelechelic polybutadiene (HTPB) and poly(ethylene glycol) (PEG) have been investigated as a function of temperature and CO₂ pressure by combining in situ near-infrared spectroscopy with molecular modeling. The results reported here for the PEG−CO₂ system are in a very good agreement with literature data hence validating our experimental procedure. It has been found that CO₂ sorption and swelling effect is more important for PEG than for HTPB. For both polymers, an increase of temperature leads to a strong decrease of both the CO₂ sorption and swelling. In order to identify at a molecular level the nature and strength of intermolecular interaction occurring between CO₂ and the polymers, ab initio calculations have been performed on model structures, representative of the main functional group of the polymer, and their complex with CO₂. Trans-3-hexene (3-Hex), propyl methyl ether (PME) and methoxytrimethylsilane (MTMS) have been selected to mimic the functional groups of HTPB, PEG and polydimethyl siloxane (PDMS), respectively. The last system has been chosen since previous works on the swelling of PDMS by high pressure CO₂ have revealed the high ability of CO₂ to swell both uncrosslinked and crosslinked PDMS. The calculated stabilization energies of the MTMS−CO₂, PME−CO₂, and 3-Hex−CO₂ dimers indicate that CO₂ interacts specifically with the three moieties through a Lewis acid−Lewis base type of interaction with the energies displaying the following order: E(MTMS−CO₂) = −3.59 > E(PME−CO₂) = −3.43 > E(3-Hex−CO₂) = −2.5 kcal/mol. Since the solubility of CO₂ in the corresponding homopolymers follows the same order, it is evidenced that the stronger the interaction between CO₂ and the polymer, the higher the CO₂ sorption. Therefore, even if one cannot exclude the influence of free volume and chain flexibility of the polymer, it appears that the solubility of CO₂ in the polymer is predominantly governed by the interaction between CO₂ and the polymer. Although the same trend is observed for the swelling of the polymer as a function of the CO₂ pressure, we have found that for a given value of CO₂ sorption, the swelling of the polymer depends on its nature, meaning that the swelling is not only governed by the CO₂−polymer interaction but also by other intrinsic properties of the polymer.< Réduire