New fluoro derivatives of Ph2N-containing (Ph: phenyl) oligo(arylenevinylene) derivatives are prepared by using double Heck-coupling reactions or Horner–Wadsworth–Emmons reactions. These oligomers are highly fluorescent (fluorescence quantum yields Φ = 0.93–0.68) with emissions in a broad wavelength region (448–579 nm), depending on the position of the fluoro substituents. The highest occupied and lowest unoccupied molecular orbital (HOMO–LUMO) energy levels of these oligomers are characterized by electrochemistry and UV spectroscopy. The effects of the fluoro substituents on the energy levels are rationalized with HOMO–LUMO simulations. In a classical organic light emitting diode (OLED), one representative (5a) shows a remarkable external quantum efficiency value (ηext = 4.87 %) at J = 20 mA cm–2; the maximum brightness at 10.2 V is 22 506 cd m–2 (λ = 458 nm; Commission Internationale de l'Eclairage (CIE) coordinates x = 0.14, y = 0.14) with a full width at half-maximum of 54 nm, demonstrating the superiority of these fluoro-containing oligomers in OLED devices.