A novel hybrid mesoporous aerogel of syndiotactic polystyrene (sPS) and silica with dual network structures was synthesized by a two-step method. First, the sPS gel was prepared using typical thermoreversible gelation procedure. Second, the silane precursor was absorbed inside the macropores of sPS network and converted to silica gel using acid-base catalyzed sol-gel reactions. The ratio of silane to sPS was varied in this work. The hybrid aerogel was recovered by supercritical drying in carbon dioxide. The method combined mesoporous hydrophilic silica with macro- and micro-porous hydrophobic sPS in single materials. This unique combination of organic and inorganic materials and their associated surface area and surface energy offers attractive properties. This paper shows that the ratio of sPS and silica can be used as a factor to obtain improvements in compressive modulus and compressive strain at break and to increase the pore surface area.