The dynamics of adsorption, interfacial tension, and theological properties of two phosphocholine-derived partially fluorinated surfactants FnHmPC, designed to compensate for the weak CO2-surfactant tail interactions, were determined at the pressurized CO2-H2O interface. The two surfactants differ only by the length of the hydrocarbon spacer (5 CH2 in F8H5PC and 11 CH2 in F8H11PC) located between the terminal perfluoroalkyl chain and the polar head. The length of this spacer was found to have a critical impact on the adsorption kinetics and elasticity of the interfacial surfactant film. F8H5PC is soluble in both water and CO2 phases and presents several distinct successive interfacial behaviors when bulk water concentration (C-W) increases and displays a nonclassical isotherm shape. The isotherms of F8H5PC are similar for the three CO2 pressures investigated and comprise four regimes. In the first regime, at low C-W, the interfacial tension is controlled by the organization that occurs between H2O and CO2. The second regime corresponds to the adsorption of the surfactant as a monolayer until the CO2 phase is saturated with F8H5PC, resulting in a first inflection point. In this regime, F8H5PC molecules reach maximal compaction and display the highest apparent interfacial elasticity. In the third regime, a second inflection is observed that corresponds to the critical micelle concentration of the surfactant in water. At the highest concentrations (fourth regime), the interfacial films are purely viscous and highly flexible, suggesting the capacity for this surfactant to produce water-in-CO2 microemulsion. In this regime, surfactant adsorption is very fast and equilibrium is reached in less than 100 s. The behavior of F8H11PC is drastically different: it forms micelles only in the water phase, resulting in a classical Gibbs interface. This surfactant decreases the interfacial tension down to 1 mN/m and forms a strongly elastic interface. As this surfactant forms a very cohesive interface, it should be suitable for formulating stable water-in-CO2 emulsions. The finding that the length of the hydrocarbon spacer in partially fluorinated surfactants can drastically influence film properties at the CO2-H2O interface should help control the formation of microemulsions versus emulsions and help elaborate a rationale for the design of surfactants specifically adapted to pressurized CO2.