Transparent and colorless epoxy/silsesquioxane (SQ) hybrids were prepared by modifying bisphenol-A epoxy resin with two SQ type epoxy resins having different 3D structures, that is, double-decker SQ and cage SQ type epoxy resins. To compare these two hybrids, the cured resin modified with the imperfect ladder SQ epoxy resin was also prepared. The effects of the 3D-structure of the SQ moieties on the thermomechanical, optical and dielectric properties of the cured epoxy/SQ hybrids were investigated. Thus, the refractive index and dielectric constant of the hybrids significantly decreased with an increase in the contents of the SQ moieties. This is due to the introduction of Si atoms with a low atomic polarity and large intermolecular space that was estimated from the difference between the volume of the space surrounded by "Connolly surface" and the van der Waals volume of the SQ moieties. The glass transition temperature, T (g), also decreased with the introduction of the SQ moieties, due to the increase in the intermolecular space. Thus, it was concluded that the performance of the epoxy/SQ hybrids depends not only on the SiO3/2 content, but also on the 3D structure of the SQ moieties.