The unusual solubility of carbon dioxide in 1-butyl-3-methylimidazolium acetate (Bmim Ac) has been studied by Raman spectroscopy and DFT calculations. It is shown that the solubility results from the existence of two distinct solvation regimes. In the first one (CO2 mole fraction <= 0.35), the usual Fermi dyad is not observed, a fact never reported before for binary mixtures with organic liquids or ionic liquids (IL). Strong experimental evidence complemented by effective DFT modeling shows that this regime is dominated by a chemical reaction leading to the carboxylation of the imidazolium ring accompanied by acetic acid formation. The reactive scheme proposed involves two concerted mechanisms, which are a proton exchange process between the imidazolium cation and the acetate anion and the carboxylation process itself initiated from the formation of "transient" CO2-1-butyl-3-methylimidazole 2-ylidene carbene species. In that sense, CO2 triggers the carboxylation reaction. Moreover, this dynamic picture circumvents consideration of a long-lived carbene formation in dense phase. The second regime is characterized by the detection of the CO2 Fermi dyad showing that the carboxylation reaction has been strongly moderated. This finding has been interpreted as due to the interaction of the acetic acid Molecules with the COO group of acetate anions involved in monodentate forms with the cation. The observation of the Fermi doublet allows us to infer that CO2 essentially preserves its linear geometry and that the nature and strength of the interactions with its environment should be comparable to those existing in organic liquids and other IL as well These results have been supported by DFT calculations showing that the CO2 molecule interacts' with energetically equivalent coexisting structures and that, its geometry departs only slightly from the linearity. Finally, we find that the CO2 solvation in Bmim Ac and 1-butyl-3-methylimidazolium trifluoroacetate (Bmim TFA) cannot be straightforwardly compared neither in the first regime due to the existence of a chemical reaction nor in the second regime because CO2 interacts with a variety of environments not only consisting of ions pairs like in Bmim TFA but also with carboxylate and acetic acid molecule.