Organic-inorganic polymer hybrids were prepared utilizing pi-pi interactions. The sol-gel reaction of phenyltrimethoxysilane (PhTMOS) was carried out in the presence of an acrylate polymer having a triphenylimidazole moiety such as poly(4-(4,5-diphenyl-1H-imidazol-yl)-phenyl acrylate-co-methyl methacrylate) (PDM). Transparent and homogeneous polymer hybrids were obtained from PDM and alkoxysilanes having aromatic groups such as PhTMOS. These polymer hybrids could be obtained in a wide range of mass ratios of PDM/PhSiO1.5 = 9/1-4/6. In these polymer hybrids, the pi-pi interaction played an important role in the dispersion of PDM in the PhSiO1.5 matrix.