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Low dielectric constant nanocomposites of polyimides with grafted methacrylate side chains containing polyhedral oligomeric silsesquioxane (POSS) were successfully synthesized by thermally initiated free-radical graft copolymerization of methacrylcyclopentyl-POSS (MA-POSS) with the ozone-preactivated poly(amic acid), followed by thermal imidization. The dielectric constant of the film can be tuned by varying the molar ratio of the grafted MA-POSS side chains in the copolymer.