Organic light-emitting devices(OLEDs) with the structure of indium-tin-oxide(ITO)/N,N′-bis-(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine(NPB)/2,9-dimenthyl-4,7-diphenyl-1,10-phenanthroline(BCP)/tris(8-hydroxyquinoline)aluminum(Alq3)/Mg:Ag or that of ITO/NPB/1,2,3,4,5,6-hexakis(9,9-diethyl-9H-fluoren-2-yl)benzene(HKEthFLYPh)/Alq3/Mg:Ag were studied. White light emission was achieved with the two devices when the thicknesses of BCP and HKEthFLYPh were 1.5 nm(device B) and 5 nm (device II), respectively. The obvious difference was that the EL spectrum of device II was not sensitive to the thickness of HKEthFLYPh compared to that of BCP layer. Moreover, the maximum luminance of device II was about 1000 cd/m2 higher than that of device B at a forward bias of 15 V, and it exhibited a maximum power efficiency of 1.0 lm/W at 5.5 V, which is nearly twice that of device B. The performance of device II using a novel star-shaped hexafluorenylbenzene organic material was improved compared with that of BCP.