Semiconducting polymers, particularly of the third generation, including donor-acceptor (D-A) copolymers, are extensively studied due to their huge potential for photonic and electronic applications. Here, we report on two new D-A copolymers, CP1 and CP2, composed of different electron-donor (D) units: 9-(2-ethylhexyl)carbazole or dibenzothiophene-5,5-dioxide, respectively, and of 4,7-bis(4'-(2-octyldodecyl)thiophen-2'-yl)-5,6-difluorobenzo[c][1,2,5]thiadiazole building block with central 5,6-difluorobenzo[c][1,2,5]thiadiazole electron-acceptor (A) units, which were synthesized by Suzuki coupling in the high-boiling solvent xylene and characterized. The copolymers exhibited very good thermal and oxidation stability. A copolymer CP1 with different molecular weights was prepared in order to facilitate a comparison of CP1 with CP2 of comparable molecular weight and to reveal the relationship between molecular weight and properties. The photophysical, electrochemical, and electroluminescence properties were examined. Intense red photoluminescence (PL) with higher PL efficiencies for CP1 than for CP2 was observed in both solutions and films. Red shifts in the PL thin film spectra compared with the PL solution spectra indicated aggregate formation in the solid state. X-ray diffraction measurements revealed differences in the arrangement of molecules in thin films depending on the molecular weight of the copolymers. Light-emitting devices with efficient red emission and low onset voltages were prepared and characterized.