This work presents a novel approach using supercritical carbon dioxide (SCCO2) to selectively extract poly(propylene glycol) (PPG) porogen from a poly(methylsilsesquioxane) (PMSSQ) matrix, which results in the formation of nanopores. Nanoporous thin films were prepared by spin-casting a solution containing appropriate quantities of PPG porogen and PMSSQ dissolved in PM acetate. The as-spun films were thermally cured at temperatures well below the thermal degradation temperature of the organic polymer to form a cross-linked organic/inorganic polymer hybrid. By selectively removing the CO2 soluble PPG porogen, open and closed pore structures are possible depending upon the porogen load and its distribution in the matrix before extraction. In the present work, two different loadings of PPG namely 25 wt.% and 55 wt.% were used. Both static SCCO2 and pulsed SCCO2/cosolvent treatments were used for PPG extraction. The initial results indicate that the pulsed SCCO2/cosolovent treatment was more efficient. Fourier transform infrared spectroscopy (FTIR) and refractive index measurements further corroborate the successful extraction of the porogens at relatively low temperatures (2000C). For the pure PMSSQ film, the k value is 3.1, whereas it is 1.46 and 2.27 for the open and closed pore compositions respectively after the static SCCO2 extraction and 430°C subsequent annealing. The reduction in the k-value is attributed to the formation of nanopores. The pore structure was verified from transmission electron microscopy (TEM), and from small-angle x-ray scattering (SAXS) measurements, the pore size was determined to be 1-3 nm for these films.