This study describes the synthesis and characterization of four polymers based on benzo[1,2-b:4,5-b']dithiophene (BDT) and isoindigo with zero, one, two, and three thiophene spacer groups. Results have demonstrated that the use of bithiophene as a spacer unit improves the geometry of the polymer chain, making it planar, and hence, potentially enhanced π- π stacking occurs. Due to favorable interaction of the polymer chains, enhanced absorption coefficient, and optimal morphology, PBDT-BTI, which possesses bithiophene as a spacer, revealed high current and fill factor leading to a power conversion efficiency of 7.3% in devices, making this polymer the best performing isoindigo-based material in polymer solar cells (PSCs). Also, PBDT-BTI could still maintain efficiency of over 6% with the active layer thickness of 270 nm, making it a potential candidate for a material in printed PSCs. These results demonstrate that the use of thiophene spacers in D-A polymers could be an important design strategy to produce high-performance PSCs.