Synthesis of nanoporous ceramic materials by surfactant templating provides opportunities to control pore size, shape, and functionalization for advanced materials applications. Ordered silica material is synthesized through a co-assembly process, in which the hydrophobicity of the surfactant tail group drives the formation of the mesophase, while the hydrolyzed silica precursor associates with the surfactant head group. Polymerization of the precursor and subsequent surfactant removal results in pore structures that mimic the surfactant mesophase. We have demonstrated the ability to tune pore size of fluorocarbon surfactant templated nanoporous silica thin films and precipitated particles using compressed and supercritical CO₂. Compressed CO₂ results in a significant increase in pore diameter for cationic fluorinated surfactant templated materials due its favorable interactions with the ‘CO₂-philic' fluorinated tail. In-situ fluorescence spectroscopy is used to monitor the dynamic changes in the film structure in the presence of CO₂ and to interpret the difference in pore size increase observed for hydrocarbon and fluorocarbon templates. The structures of the fluorescent probes are tuned to preferentially localize them in either the hydrophobic interior of the micelles or at the ionic silicate-tail interface and their responsiveness to CO₂ pressure is demonstrated. A significant increase in the time period of modulable steady state (MSS), indicating delayed condensation of silica structure, is observed in the presence of CO₂. The results suggest time scales and approaches to further refine the nano-structured materials (i.e., infuse pores with reactive agents, functionalize pores, and reorient functional groups within the pores) using CO₂ processing.