The synthesis of surfactant templated thin films in the presence of supercritical (sc) CO₂ can be used to capture and interpret the pressure-tunable effects of CO₂ on surfactant mesophases. Significant differences in the penetration of sc CO₂ in fluorocarbon and hydrocarbon surfactant mesophases has been observed through processing of the respective surfactant templated films in sc CO₂ immediately after casting. The ability to tailor CO₂-induced pore expansion is compared for fluorinated and hydrocarbon pyridinium chloride surfactants (cetyl pyridinium bromide (CPyB); 1-(3,3,4,4,5,5,6,6,7,7,8,8, tridecafluorooctyl) pyridinium chloride (HFOPC) and 1-(11,11,12,12,13,13,14,14,15,15,16,16, tridecafluorocetyl) pyridinium chloride (HFCPC)). CPyB and HFCPC have equal number of carbons in the surfactant chain. HFOPC and HFCPC have an identical number of fluorocarbon groups (-C₆F₁₃) but differ by the number of hydrocarbon spacers (-C₂H₄- and –C₁₀H₂₀-, respectively). Well-ordered thin films with 2D hexagonal pore structure are obtained for both unprocessed films and CO₂-processed films (69 – 172 bar and 25^oC - 45^oC for 72 hours). HFOPC templated films underwent large pore expansion (varying between 20% - 45%) compared to unprocessed films with increase of CO₂ pressure while a slightly lesser degree of pore expansion was observed for HFCPC templated films. However for both hydrocarbon surfactant templates, negligible pore size increase was observed on CO₂ processing. The large degree of pore expansion observed for fluorinated surfactant templated films results from significant penetration of small CO₂ molecules in the fluorinated tail due to favorable interactions between CO₂ and ‘ CO₂-philic' fluorinated moieties arising from their similar cohesive energy densities and low surface tension. Simulation and experimental studies have previously compared CO₂ penetration in fluorinated and hydrocarbon tail in microemulsion systems and at CO₂-water interfaces. However, the current experiments are the first to directly compare CO₂-induced swelling in fluorinated and hydrocarbon surfactant mesophases. This work also demonstrates the ability to tailor the pore size in mesoporous silica thin films without loss of ordering by combining the tunable solvent strength of compressed and sc CO₂ and fluorinated surfactants.