A white light polymer light-emitting diode was demonstrated with a double layer configuration: poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine] (poly-TPD) blended with poly(N-vinylcarbazole) as both hole-transporting layer and electron-blocking layer, blue-emissive poly(9,9-dihexylfluorene-alt-co-2,5-dioctyloxy-para-phenylene) (PDHFDOOP) blended with green-emissive poly[6,6'-bi-(9,9'-dihexylfluorene)-co-(9,9'-dihexylfluorene-3-thiophene-5'-yl)] as an emissive layer. By annealing the emissive layer at a relatively high temperature, fluorenone defects were generated into PDHFDOOP, which formed an exciplex with poly-TPD, as a red emitter. The devices exhibit a maximum brightness of ~4800 cd/m2 and a maximum luminous efficiency of ~3 cd/A. Moreover, the Commission Internationale de L'Eclairage coordinates of the emitted light is close to that of pure white light and is insensitive to the applied voltages.