To investigate the fine optoelectronic difference of the target oligomers with or without peripheral fluorene moieties, two dumbbell-shaped oligomers (F0 and F1) were designed and convergently prepared via Suzuki coupling reaction. The molecular structures of the oligomers were fully characterized by H-1 NMR, C-13 NMR, and MALDI-TOF mass spectra, respectively. The absorption, photoluminescent behavior, and energy band gaps of the oligomers were examined through UV-vis, photoluminescent spectra and cyclic voltammetry. The experimental results demonstrate that the absorption and photoluminescent properties are little affected by molecular architecture, while the absolute photolumineseence quantum efficiency of films and energy band gaps derived from cyclic voltammetry in solution are strongly correlated with the molecular frameworks. The observed energy band gaps of oligomers are further validated by the different molecular orbital contours of the HOMO energy levels from theoretical calculations. Preliminary electroluminescent investigations for F1 have also been conducted and discussed. (C) 2008 Wiley Periodicals, Inc.