Polyhedral oligomeric silsesquioxanes (POSS) were used as starting materials for the preparation of hybrid materials with polystyrene (PS). Optically transparent hybrids were obtained in a wide range of weight ratios when phenyl groups were introduced to each corner of the silsesquioxane. In contrast, as cyclohexyl groups were introduced, the obtained hybrid materials with PS resulted in turbid films. The aromatic (π-π) interaction was confirmed to be a quite effective tool for the synthesis of organic-inorganic polymer hybrids with POSS. The obtained homogeneous and transparent hybrid films could be dissolved in solvents and cast again without any separation. The homogeneity of polymer hybrids with POSS was supported by the result of scanning electron microscopy (SEM), X-ray diffraction (XRD), and differential scanning calorimetry (DSC), which demonstrated a nanometer-level integration of PS and POSS.