Polyimide-tethered polyhedral oligomeric silsesquioxane, (R7R'Si8O12) (POSS), nanocomposites with well-defined architectures are prepared by the copolymerization reaction of a new type of diamine monomer: POSS-diamine, 4,4'-oxydianiline (ODA), and pyromellitic dianhydride (PMDA). This type of polyimide-side-chain-tethered POSS nanocomposite presents self-assembly characteristics when the amount of POSS exceeds 10 mol %, as evidenced by transmission electron microscopy studies. Furthermore, POSS/polyimide nanocomposites have both lower and tunable dielectric constants, with the lowest value of 2.3, and controllable mechanical properties, as compared to that of pure polyimide.