A series of high molecular weight fluorene-based soluble poly(arylene ethynylene)s (PAEs) have been prepared and characterized. The polymers consist of 2,5-bis(3-tetradecylthiophen-2-yl)-3a,6a-dihydrothieno[3,2-b]thiophene, 2,5-bis(3-tetradecylthiophen-2-yl)-3a,6a-dihydrothiazolo[5,4-d]thiazole, or 4,7-bis(3-tetradecylthiophen-2-yl)benzo[c] [1, 2, 5] thiadiazole unit with an electron donor 9,9-bis(2-ethylhexyl)-9H-fluorene unit connected via electron accepting ethynylene linkage. The molecular weights (M (w)) of the polymers were found to be in the range of 103600-179000 g/mol with polydispersity index (PDI) of 3.9-5.0. Optical and redox properties have been investigated by UV-visible, fluorescence spectroscopy, and cyclic voltammetry (CV) measurements. Combination of experimental and density functional theory (DFT) calculations indicated that the benzothiadiazole unit incorporated polymer has lowest band gap with most stable lowest unoccupied molecular orbital (LUMO) energy level. Polymer light emitting diode properties have been investigated for the polymer having highest molecular weight with device configuration ITO/PEDOT:PSS/Polymer/LiF/Al. Well-behaved diode characteristics with EL maxima at 600 nm were observed.