This work focuses on the design of unique “cage–cage” shaped low dielectric constant and hydrophobic materials with nano-sized pores and few polarizable groups. Therefore, a novel double-decker structural fluorinated POSS was first synthesized, which then reacted with a diphenol POSS to produce linear hybrid polymers. When the merits of fluoride and nanoporous structures are combined, the dielectric constant of the hybrid material decreases significantly (2.24 at 1 MHz) and a low surface energy (contact angle of 107° in water) of the material, as well as good solubility and thermal properties are obtained.