Anionic poly(p-phenylene-ethynylene) (PPE) incorporated polymer hybrids were synthesized from the PPE and tetramethoxysilane together with the organic polymers such as poly(vinylpyrrolidone) via a sol-gel method. Up to 10 wt % of the anionic PPE could be dispersed homogeneously in the resulting polymer hybrid matrix. The obtained polymer hybrids exhibited controllable photoluminescence properties by the modification of the internal environment of organic-inorganic polymer hybrids by changing the organic/inorganic ratios. The photoluminescence of the anionic PPE surrounded by the polymer hybrid matrix was reinforced against the thermal irradiation. Moreover, the photoluminescence of the obtained organic-inorganic polymer hybrids was also tuned by utilizing ionic interactions between the anionic PPE and the inorganic matrix. (C) 2008 Wiley Periodicals, Inc.