Nanoporous poly(methyl silsesquioxane) (PMSSQ) was obtained by sintering organic/inorganic nanohybrids. The porogen was cyclosiloxane with four poly(ethylene glycol) arms for better miscibility with PMSSQ. As the porogen content in the hybrid increased up to 30 vol%, the porosity of the calcined PMSSQ film increased up to 24%, and the k values decreased as low as 2.12. However, the interconnected pore structure was observed at the porogen content above 25 vol%. The miscibility was improved compared to poly(caprolactone)-based porogens and the pore size was indistinguishable even at SEM resolution.