A series of blue electroluminescent polyfluorenes (PFs) containing triphenylamine and various alkyl moieties were synthesized using an Ni(0) mediated C−C Yamamoto coupling reaction assisted by microwaves. The synthesized PFs were characterized by various spectroscopic techniques. Their absorption and photoluminescence properties were investigated in solvent and found to possess characteristic electronic absorption and emission spectra. These PFs were found to emit in the blue region (407−415 nm) with high quantum yield in the range 0.41−0.73. Cyclic voltammetry studies of the PFs revealed that the compounds were stable under redox conditions with highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital in the range 5.24-5.29 eV and 1.98−2.01 eV, respectively. The E HOMO for the PFs was similar to the most widely used hole transporting materials N,N ′ -Di(1-naphthyl)-N,N ′ -diphenyl-(1,1 ′ -biphenyl)-4,4 ′ -diamine (NPD), N,N ′ -Bis(3-methylphenyl)-N,N ′ -diphenylbenzidine (TPD) and N 2 ,N 2 ,N 2′ ,N 2′ ,N 7 ,N 7 ,N 7′ ,N 7′ -octakis(4-methoxyphenyl)-9,9 ′ -spirobi[9H-fluorene]-2,2 ′ ,7,7 ′ -tetramine, Spiro-OMeTAD (spiro-OMe-TAD). The thermal stability observed for the PFs accounts for their use under ambient conditions. The electrochemical studies of the fabricated polymer light emitting diodes suggest that the PFs have potential to be used as hole transporting and blue electroluminescent materials for optoelectronic devices.