Two dimeric trimeric phenylenvinylene derivative 2, 5, 2', 5'-tetrakis (4'-fluorostyryl) biphenyl (P-F-TSB) and 2, 5, 2', 5'-tetra (p-trifluoromethylstyryl)-biphenyl (TFM-TSB) have been synthesized as new electroluminescent (EL) materials. P-F-TSB exhibits good color purity, high luminance of blue light-emission in organic light-emitting devices. Maximum brightness and luminous efficiency are of 1828 cd/m2 and of 1.92 cd/A, respectively. CIE coordinates are x=0.20 and y=0.22. Interestingly, we can fabricate single layer white light-emitting device using TFM-TSB as emitting layer. The broad electroluminescence emission band may attribute to long-wavelength excimer and electromer emission in addition to the blue component from singlet excited state of individual TFM-TSB molecule. Furthermore, white-light emission can also be obtained with a typical three-layer structure of ITO/ NPB (50 nm)/ TFM-TSB (50 nm)/ Alq3 (30 nm)/LiF/Al device. The maximum brightness of this device is 809 cd/m2 at 217 mA/cm2 and 13V, and the maximum luminous efficiency is 1.49 cd/A at 11 mA/ cm2 and 8V.