This paper deals with the development of materials without volume change in the formation of uniform low density foam capsules with fine structures. Two monomers, i.e., 5-(4-vinylbenzyl)oxymethyl-5-methyl-1,3-dioxane-2-thione (M1) and 4-vinylphenyloxirane (M2), were prepared as the comonomers polymerized with styrene. Polystyrene-based copolymers using styrene and M1 or M2 were prepared by free radical copolymerization using azobis(isobutyronitrile) (AIBN) as an initiator. The solutions of the obtained polystyrene-based copolymers in benzene/dichloromethane mixture or 4-chlorotoluene were gelated by the addition of a cationic initiator, which caused cross-linking via ring-opening polymerization of the pendant cyclic moieties. The gel was transformed into an aerogel by exchanging solvent to 2-propanol, and removal of 2-propanol using supercritical CO2. SEM images of a cross sectional view of the aerogel indicated that sub-micrometer voids were distributed randomly, and most of parts look filled bulk morphology. The density of the gel obtained from the present polystyrene-based copolymers was estimated to be 200 mg/cm , which implies existence of vacancies without observation in the SEM image, suggesting the extremely fine cell structure.