The hybrid nanocomposites of poly(sodium 4-styrenesulfonate)(PSS) and octafunctional polyhedral oligomeric silsesquioxane (POSS)(Cube-aminopropyl) were prepared using Cube-aminopropyl as a cross-linker at various weight ratios. Ionic interactions between PSS and Cube-aminopropyl played a critical role in the formation of new hybrid gels with Cube-aminopropyl. The nanocomposites obtained were insoluble in organic or aqueous solvents. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the hybrid gels were comprised of three-dimensional network structures derived from Cube-aminopropyl as a cross-linker.