Three generations of novel dendrimers (G1, G2, and G3) with an electron-deficient fluorinated starburst oxadiazole core and twisted carbazoles as dendrons were synthesized via aromatic nucleophilic substitution reaction at ambient temperature by the weak base potassium fluoride with a high selectivity in a nearly quantitative yield, which was attributed to the high reactivity of the para fluorine atom activated by oxadiazole and multiple fluorine atoms. H-1. NMR, F-19 NMR, elemental analysis, and MALDI-TOF MS results confirmed the designed chemical structures. Varying the generation to gradually modify the dendrons could gradiently modulate the HOMO-LUMO energy band gaps of Gn, which was verified by cyclic voltammetry results. Photoluminescent spectra showed the dual fluorescence emission of the dendrimers in solutions, which indicated that twist intramolecular charge transfer occurred between oxadiazole and carbazole separated by nonconjugated bonds. The Gn-based devices with the configuration of ITO/PEDOT:PSS/Gn/TPBI/AlQ/LiF/Al displayed a stable green emission in their electroluminescent spectra with a gradual increase in external quantum efficiency and current efficiency for higher-generation dendrimers, owing to gradually improved charge transport. The device with G3 possessed the lowest turn-on voltage along with the highest external quantum efficiency of 1.49%, maximum current efficiency of 4.6 cd/A, and a high luminance of 4882 cd/m(2), indicating that it had the best carrier balance.