The carbon and fluorine chemical shifts of mixtures of carbon dioxide and Krytox, a carboxylic acid end-capped perfluorinated polyether used as stabilizer for the dispersion polymerization of methyl methacrylate, have been studied using high-pressure, high-resolution nuclear magnetic resonance. 13C and 19F spectra were measured in the density region between 0.54 and 0.73 g.cm(-3) at 334 K for different solutions of Krytox in scCO2 (0.22, 1.13 and 1.72 w/w %). An in-house developed high-pressure apparatus with the capability to change in situ the sample composition was used for this purpose using a 10 mm polyether ketone NMR tube. The nature of CO2-Krytox interaction was assessed both by comparing the CO2 deltaC variation of neat CO2 with that of mixtures with increasing surfactant composition and by the analysis of Krytox 19F corrected chemical shifts in terms of medium magnetic susceptibility. Ab initio calculations, at the second-order Møller-Plesset level of theory to include the effects of electron correlation, were performed to access and compare the nature of the interactions between CO2 and perfluorinated and nonfluorinated analogue model molecules. Both experimental 13C and 19F HP-NMR results and molecular modeling studies support a F...CO2 site-specific Lewis acid-Lewis base interaction model. A positive entropic variation for the formation of CO2-fluorinated solute complex is advanced as an explanation for the higher solubility of perfluorinated molecules when compared to the nonfluorinated analogues.