Novel polyfluorene copolymers with pendant hydroxyl groups, poly[2,7-(9,9-dihexylfluorene)-2,7-(9,9-bis(6-hydroxyhexyl)fluorene)-co-2,7-(9,9-dihexylfluorene)-1,4-phenylene] (PFP-OH) and poly[2,7-(9,9-dihexylfluorene)-2,7-(9,9-bis(6-hydroxyhexyl) fluorene)-co-2,7-(9,9-dihexylfluorene)-4,7-(2,1,3-benzothiadiazole)] (PFBT-OH) were prepared. Acid-catalyzed polycondensations of tetraethoxysilane were carried out in the presence of these polymers to obtain homogeneous hybrids. Photoluminescence spectra of these hybrids suggested the polymers were immobilized in silica matrix retaining their pi-conjugated structures. Further, hybrids of coat film were prepared utilizing perhydropolysilazane as a silica precursor. Their optical properties were examined. (C) 2010 Wiley Periodicals, Inc. J PolymSci Part A: Polym Chem 48: 5322-5328, 2010