The strong desire for the extensive application of supercritical carbon dioxide (scCO(2)) as an environmentally benign solvent in polymers synthesis and processing has spurred numerous attempts to discern and improve its solvability toward monomers as well as polymers. The detailed solvation processes along with the phase behaviors of a fluorinated liquid monomer (LM) of 2,2,2-trifluoroethyl methacrylate (TFEMA), as well as another 13 non-fluorinated LMs in gaseous and supercritical CO2, were respectively investigated by using a newly built high-pressure ATR-FTIR in situ monitoring system as CO2 pressure stepwise increased from 0 to 38.0 MPa. Interestingly, an unexpected vibrational absorption variation, especially a distinct blue-shift in the in situ FTIR spectra of the functional groups in each LM + CO2 binary system, was generally observed during the solvation process as CO2 pressure increased. A similar variation trend of the vibrational absorption of the C F bond in the TFEMA + CO2 system was also obtained by ab initio calculation (MP2). We believe that the special evolution of the vibrational absorption is directly rooted in and dynamically induced by the variation of the intermolecular interactions in the LM + CO2 binary systems as the pressure and/or the temperature varied and is closely related to the solvation behaviors of the LM in CO2. :Based on this cognition, the solvation mechanism of the LMs in gaseous and supercritical CO2 was systematically demonstrated by introducing the concepts of transition pressure (P-T) as well as the resultant forces/interactions of sigma(A-B) and sigma(B-B). Poly(vinyl acetate) (PVAc), poly(hexafluoropropylene oxide) (PHFPO), and FTFEMA oligomers were prepared and characterized. The proposed mechanism was evaluated by investigating the solvation behaviors of the prepared oligomers and hexafluoropropylene trimer ((HFP)(3)) in CO2 and was successfully employed to expound the special CO2-philicity of the carbonyl compounds and the fluorinated organics (FOs).