The aim of this study was to elucidate the catalytic partial oxidation of propane to oxygenates on vanadyl pyrophosphate ((VO)(2)P2O7) in dense carbon dioxide acting as a solvent. The reaction was carried out in continuous flow experiments at 673 K at a molar ratio of CO2:synthetic air:propane of 86:13:1, a residence time of 19 s and sub- to supercritical pressures ranging from 2.4 to 9.7 MPa. The catalytic tests revealed the formation of acrylic and acetic acid besides total oxidation products. The selectivity to acetic acid increased with rising pressure, whereas that of acrylic acid decreased. These results may be attributed to a diverging adsorption of both the oxygenates with pressure, which was investigated by supercritical fluid chromatography. Additionally, critical data of both the reaction feed and the product mixture were determined in a high-pressure optical cell by the opalescence method.