Carbon dioxide sequestration is one of many mitigation tools available to help reduce carbon dioxide emissions while other disposal/repurposing methods are being investigated. Geologic sequestration is the most stable option for long-term storage of carbon dioxide (CO₂), with significant CO₂ trapping occurring through mineralization within the first 20-50 years. A fiber optic based monitoring system has been proposed to provide real time concentrations of CO₂ at various points throughout the geologic formation. The proposed sensor is sensitive to the refractive index (RI) of substances in direct contact with the sensing component. As RI is a measurement of light propagating through a bulk medium relative to light propagating through a vacuum, the extraction of the effects of any specific component of that medium to the RI remains very difficult. Therefore, a requirement for a selective barrier to be able to prevent confounding substances from being in contact with the sensor and specifically isolate CO₂ is necessary. As such a method to evaluate the performance of the selective element of the sensor was investigated. Polybenzimidazole (PBI) and VTEC polyimide (PI) 1388 are high performance polymers with good selectivity for CO₂ used in high temperature gas separations. These polymers were spin coated onto a glass substrate and cured to form ultra-thin (>10 μm) membranes for gas separation. At a range of pressures (0.14 –0.41 MPa) and a set temperature of 24.2±0.8 °C, intrinsic permeabilities to CO₂ and nitrogen (N₂) were investigated as they are the gases of highest prevalence in underground aquifers. Preliminary RI testing for proof of concept has yielded promising results when the sensor is exposed exclusively to CO₂ or N₂. However, the use of both PBI and VTEC PI in these trials resulted in CO₂ selectivities of 0.72 to 0.87 and 0.33 to 0.63 respectively, for corresponding feed pressures of 0.14 to 0.41 MPa. This indicates that both of the polymers are more selective for N₂ and should not be used in CO₂ sensing applications as confounding gas permeants, specifically N₂, will interfere with the sensing element.