Foam is used in CO2-enhanced oil recovery due to its potential high benefits in mitigating all three causes of CO2 poor sweep efficiency, as it provides a means to lower the effect of permeability heterogeneity, overcome viscous instability, and minimize the occurrence of gravity override. The conventional foaming surfactants are not suitable in contact with oil due to premature lamellae rupture, need for copious amounts of water to generate foam, surfactant loss due to adsorption on the rock or partitioning between water and oil, and less tolerance against salinity, pressure, and temperature. The surfactant blending and addition of CO2-philic functionalities in surfactant structure are suggested to mitigate the above problems, enhance foam stability, improve mobility control, and accelerate foam propagation. However, there is a lack of general guidelines on the evaluation of CO2-philic surfactant properties and applications and the surfactant structure performance analysis. In the present work, tailor-made laboratory tests and simulation analysis were conducted on CO2-philic surfactants with different structures and chain lengths in conditions close to a Malaysian reservoir case and in the presence of oil. The results from experiments combined with analytical analysis of foam flow parameters are used to provide a comprehensive simulation model of a CO2-philic surfactant alternating gas process. A meaningful correlation between the CO2-philic surfactant structure and the sensitivity of foam model to different parameters was observed. On the basis of sensitivity analysis results, optimization of CO2-philic surfactant activity at gas-water and oil-water interfaces can improve the system recovery through macroscopic and microscopic displacement.