We report the preparation of a new class of organic/inorganic hybrid aerogels from aryl-bridged polysilsesquioxanes . l,4-Bis(triethoxysilyl)benzene and 4,4'-bis(triethoxysilyl)-biphenyl were sol-gel processed to form phenyl- and biphenyl-bridged polysilsesquioxane gels (Figure 1, structures 1 and 2, respectively). The gels were then dried using supercritical carbon dioxide extraction. It was discovered that aryl-bridged polysilsesquioxane aerogels are indeed formed, but with a pronounced influence on surface area from the reaction conditions used in preparing the initial gels. Specifically, high surface aerogels ( up to 1750 m2/g) are obtained from gels prepared with either acid or base catalysts. With reduced concentrations of base catalyst, however, supercritical processing afforded phenyl-bridged xerogel-like materials, The materials were characterized by nitrogen sorption surface analysis, and by transmission electron microscopy.