Polyfluorene (PF)-based light-emitting diodes (LEDs) typically exhibit device degradation under operation with the emergence of a strong low energy emission band (at similar to2.2-2.4 eV). This longer wavelength band converts the desired blue emission to blue-green or even yellow. We have studied both the photoluminescence (PL) and electroluminescence (EL) of PFs with different molecular structures and found that the low-energy emission band originates from fluorenone defects which are introduced by photo-oxidization, thermal oxidation, or during device fabrication. X-ray photo-emission spectroscopy (XPS) results show that the oxidation of PF is strongly catalyzed by the presence of calcium. The fluorenone defects generate a stronger contribution to the EL than to the PL. By utilization of a novel electron-transporting material as a buffer layer between the emissive PF and the Ca/Ag (Ba/Ag) cathode, the blue EL emission from the PF was stabilized.