Poly(p-phenyleneethynylene) (PPE) and silica gel polymer hybrids were synthesized from the PPE together with tetramethoxysilane (TMOS) via a sol-gel method by utilizing cationic groups on the side chain of PPEs. Up to 10 wt % of the cationic PPE was able to disperse homogeneously into a silica matrix without any compatibilizer. Compared to amino and ammonium groups, PPE having imidazolium groups exhibited high dispersity in silica gel. The photoluminescence of the cationic PPE was reinforced against the thermal irradiation by the surrounding polymer hybrid matrix.