Homogeneous polystyrene and silica gel polymer hybrids were prepared by in-situ radical polymerization method. Styrene monomer was introduced into a sol-gel reaction mixture of tetramethoxysilane (TMOS) and the polymerization was initiated by Azobisisobutyronitrile (AIBN), while sol-gel reaction of TMOS proceeded to form a silica gel. The homogeneity of the hybrids was found to be dependent on the amount of the acid catalyst. The homogeneity was confirmed quantitatively by measuring porosity of charred hybrids with nitrogen porosimetry method. It was found that polystyrene was dispersed at a nano-meter level in the silica gel matrix.