A novel polyimide (PI) hybrid nanocomposite containing polyhedral oligomeric silsesquioxane (POSS) with well defined architecture has been prepared by copolymerization of octakis(glycidyldimethylsiloxy)octasilsesquioxane (Epoxy-POSS), 4,4'-oxydianiline diamine (ODA), and 4,4'-carbonyldiphthalic anhydride (BTDA). In these nanocomposite materials, the equivalent ratio of the Epoxy-POSS and ODA are adjustable, and the resultant PI-POSS nanocomposites give variable thermal and mechanical properties. More importantly, we intend to explore the possibility of incorporating POSS moiety through the Epoxy-POSS into the polyimide network to achieve the polyimide hybrid with lower dielectric constant (low-k) and thermal expansion. The lowest dielectric constant achieved of the POSS/PI material (PI-10P) is 2.65 by incorporating 10 wt% Epoxy-POSS (pure PI, k = 3.22). In addition, when contents of the POSS in the hybrids are 0, 3, 10 wt% (PI-0P, PI-3P, PI-10P), and the resultant thermal expansion coefficients (TEC) are 66.23, 63.28, and 58.25 ppm/degreesC, respectively. The reduction in the dielectric constants and the resultant thermal expansion coefficients of the PI-POSS hybrids can be explained in terms of creating silsesquioxane cores of the POSS and the free volume increase by the presence of the POSS-tethers network resulting in a loose PI structure. (C) 2004 Elsevier Ltd. All rights reserved.