A set of anthracene containing polyfluorenes (PFs) having 9,10-diphenylanthracene with alkyl substituents and aniline containing fluorenes were prepared. Commonly, light-emitting polymers were synthesized using expensive palladium-like catalysts. In the present work, palladium was replaced by copper as a cost-effective PF synthesis catalyst, which is also suitable for large-scale polymer synthesis. Synthesized PFs emit light in the blue region with a bandgap of 2.87–2.90 eV. Thermally stable PFs had a decomposition temperature of more than 305C and a glass transition temperature of 125–138C. PFs were soluble in organic solvents and had a molecular weight of around 21,700–25,500. The electrochemical study of these PFs showed low level of highest occupied molecular orbital (HOMO)energy of5.16 to5.26 eV, which was significantly higher than that of PF (5.7 eV). These findings suggested that the resulting PFs could be used as a component of the light-emitting diode.