Three new benzodithiophene-alt-di(thiophen-2-yl)quinoxaline polymers were prepared with the aim of exploring 5,8-bis(thiophen-2-yl)-2,3-didodecyl-6,7-difluoroquinoxaline (TFQ)-based polymers on fullerene-free organic solar cells (OSCs). The electron-rich benzo[1,2-b:4,5-b']dithiophene unit contains three different substituents, namely 2,6-bis(trimethyltin)-4,8-bis(2-butyloctyloxy)benzo[1,2-b:4,b']-dithiophene (Distannyl BDTO), 2,6-bis(trimethyltin)-4,8-bis(5-(2-butyloctyl)thiophen-2-yl]benzo [1, 2-b:4,5-b']dithiophene (Distannyl BUTT), and 2,6-bis(trimethyltin)-4,8-bis(triisopropylsilylethynyl)-benzo[1,2-b:4,5-']dithiophene (Distannyl BDTSi). These were polymerized with electron deficient 5,8-bis(5-bromothiophen-2-yl)-2,3-didodecyl-6,7-difluoroquinoxaline (Dibromo TFQ) to afford the polymers P(BDTO-TFQ), P(BDTT-TFQ), and P(BDTSi-TFQ). The estimated band-gaps (E(g)s) and the highest occupied molecular orbital levels (HOMOs) were 1.88, 1.86, and 1.94 eV, and - 5.35, - 5.44, and - 5.58 eV, respectively. The OSCs made with a blend of polymer and ITIC (3,9-bis(2-methylene- (3-(1,1 -dicyanomethylene)indanone))-5,5,11,11-tetrakis(4-hexylphenyedithieno [2,3-d: 2', 3'd'-s-indaceno [1,2-b:5,6-b']dithiophene) gave the maximum power-conversion efficiencies (PCEs) of 3.49, 7.06, and 0.75%, respectively. Overall, the substituents attached at the 4- and 8-positions of the BDT unit of the TFQ-based polymers were found to exhibit greatly altered properties, such as their absorption, energy levels, and crystallinity. This resulted in dissimilar photovoltaic performance for the resulting polymers.