We show experimentally that CO2 intercalates into the interlayer spaceof the synthetic smectite clay Li-fluorohectorite (LiFh). The intercalationoccurs for a range of conditions in terms of pressure (5 bar to 20 bar) andtemperature (-20'C to 5'C). The mean basal spacing of the clay layersin LiFh intercalated by CO2 is found to be approximately 12.0 Å.We observe that the dynamics depends on the pressure, with a higherintercalation rate at increased pressure. Even under pressure of 20 bar,intercalation of CO2 is slower than H2O intercalation in fluorohectoritesby orders of magnitude.In situ observations show that LiFh is able to retain CO2 in the interlayerspace at room temperature, and the CO2 only starts leaving the clay attemperatures exceeding 30'C. Hydrated and CO2-intercalated clays areindistinguishable by use of X-ray diffraction alone. The difference in behaviorat higher temperatures is used as an additional confirmation thatintercalation of residual water is not the cause of the observed swelling.Furthermore, we report a new intercalation state corresponding to intercalationof more than one layer of CO2 into the interlamellar space, andhave also observed changes in the intercalation state of a monohydratedLiFh sample under exposure to CO2.We believe that the findings, concerning both intercalation and deintercalation,could be relevant for application of clays related to capture, transportor storage of CO2.