The ternary polymer hybrids were prepared by organic polymers such as poly(2-methyl-2-oxazoline) (POZO) or poly(N-vinylpyrrolidone) (PVP) and aminopropylsilsesquioxane (Cube-aminopropyl) utilizing the sol-gel reaction of tetramethoxysilane (TMOS). The prepared polymer hybrids were characterized by IR, thermogravimetric analysis (TGA), X-ray diffraction (XRD), H-1 NMR, scanning electron microscopy (SEM), etc. In this hybrid system, hydrogen-bonding interactions played a critical role in the formation of the transparent polymer hybrids. Polymer hybrids using POZO showed high transparency and homogeneity in a wide range of the feed ratios of POZO to Cube-aminopropyl. On the other hand, in case of polymer hybrids using PVP, higher Cube-aminopropyl ratio brought about the phase separation, indicating the aggregation of the Cube-aminopropyl itself. The homogeneity of ternary polymer hybrids was found to be closely dependent on the difference between strength of hydrogen bonding interaction of polymer and residual silanol groups of silica gel and strength of that of polymer and Cube-aminopropyl. It is also observed that initial decomposition temperature of polymer hybrids was increased with increasing the Cube-aminopropyl ratio.