Isomeric tetraphenylbenzodifuran systems, benzo-[1,2-b:5,4]difuran and benzo[1,2-b:4,5]difuran, containing electron acceptor groups (CF3, CN, and NO2) have been synthesized and studied. Their electronic absorption, fluorescence, two-photon absorption cross sections, and electrochemical properties were investigated. The absorption and emission maxima are red-shifted for the linear-conjugated systems in comparison with the corresponding isomer. Dual fluorescence was observed and the existence of a twisted intramolecular charge transfer state was confirmed by low-temperature emission experiments. Wide HOMO-LUMO energy gaps were obtained ranging from 2.53 to 3.28 eV. HOMO levels were found in the energy range of -6.03 to -6.63 eV while LUMO are within -2.55 to -3.52 eV.