The CO₂-catalyzed acetalization is regarded as a promising alternative to the conventional acid-catalyzed method from a viewpoint of green chemistry (C. A. Eckert et al., Ind. Eng. Chem. Res. 43, 2605 (2004)). We have applied in situ attenuated total reflection infrared (ATR-IR) spectroscopy for elucidating and monitoring the acetalization of cyclohexanone in CO₂-expanded ethylene glycol and methanol at 50 °C and 3 MPa. The ATR-IR spectra of the reaction mixtures periodically recorded with a ZnSe crystal demonstrate that ATR-IR spectroscopy is a practical tool for tracing the kinetics of acetalizations in situ. In addition, the rate of CO₂ dissolution as well as CO₂ solubility into the cyclohexanone–alcohol mixtures could be evaluated from the CO₂-v₃-antisymmetric stretching band. The ZnSe ATR crystal, however, was corroded during longer use under the acidic conditions realized by the dissolution of CO₂ in the alcohols. In contrast, the corrosion did not occur when a Ge crystal was used instead of a ZnSe crystal, and therefore the application of a Ge ATR crystal is recommended for continuous long-term experiments with these media.