We have synthesized polyfluorene-based copolymers containing spiro-cycloalkyl groups functionalized on the C-9 position of alternate fluorene units using the Suzuki coupling reaction. The presence of the rigid spiro-cycloalkyl pendent groups not only hinders the close packing and intermolecular interactions between polymer chains, but also preserves the molecular rigidity of the polymer, leading to polyfluorenes with high glass transition temperatures and improved thermal and spectral stabilities. The results of photoluminescence mea\surements of the isothermally heated spiro-polyfluorene thin films (150degreesC for 20h) show that the commonly observed aggregate/excimer formation is suppressed effectively in these polymers. Blue electroluminescence was demonstrated in a double-layer LED device using the spiro-derivatized polyfluorene as the emitting layer. (C) 2004 Elsevier Ltd. All rights reserved.