A series of monodisperse symmetric terfluorenes end-capped with diphenylamino groups or dendrons based on triarylamine and carbazole moieties, OF(3)R´–R, R´ = Bu or Ph, R = H, NPh, or EG, have been synthesized by a convergent approach using palladium-catalyzed Suzuki cross-coupling or copper-catalyzed Buchwald’s amination as the key reaction. The functional properties, which include thermal stabilities, linear and non-linear optical properties, and fluorescence and electrochemical properties of the terfluorene derivatives are also investigated and discussed. The preliminary results show that end-capping of the terfluorene with diphenylamino groups, especially with dendrons, has been shown to offer advantages in terms of lowering the first ionization potential, enhancing thermal stability, and inducing good amorphous morphological stability of the resulting compounds.