Well-defined electroactive bipolar derivatives of new structure have been synthesized from 3-(N,N-diphenylamino)-9H-carbazole and bis(4-fluorophenyl)sulfone, 4-fluorophenylsulfone or 4,4′-difluorobenzophenone, respectively. The full characterization of their structure is described. The amorphous materials with very high glass transition temperatures of 111–173 °C also possess high thermal stability, with onset decomposition temperatures of 351–398 °C. Some of the compounds having the best solubility were tested as the emitters dispersed in 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) host for preparation of organic light emitting diodes (OLEDs). A device containing 15 wt% of the guest bis[4-{3-(N,N-diphenylamino)carbazol-9-yl}phenyl] sulfone demonstrated the best overall characteristics with maximum brightness exceeding 2630 cd/m2, current efficiency of 3.2 cd/A, power efficiency of 2.2 lm/W, and external quantum efficiency exceeding 1.7% at 100 cd/m2
