Seven conjugated copolymers, based on dithienylbenzothiadiazole and benzene, have been synthesized with side chains placed in different position along the conjugated backbone. An additional polymer with a small modification of the investigated backbone was also included in the study. Alkoxy and alkyl side chains were considered, depending on the aromatic ring they were anchored to. Our goal was to perform an extensive study, by evaluating the possible anchoring positions of the same backbone, in order to demonstrate the huge influence of the position of side chains on a well performing polymer backbone for polymer solar cells. All the polymers were roll slot die coated under ambient conditions on flexible ITO-free plastic substrates to give inverted polymer solar cell devices with an upscaled active area of 1 cm2. The best characteristics were found for the polymer carrying alkoxy side chains on the benzene ring where power conversion efficiencies of up to 3.6% were achieved. All studied materials were prepared with an objective of low-cost starting materials, simple synthesis, and simple processing conditions which was most successful for the polymer P5. The polymer P7 containing fluorine atoms showed excellent performance under constant illumination and high temperature (exhibiting stable photovoltaic properties even after 670 h under conditions similar to ISOS-L-2 lifetime protocol). This makes P7 a good candidate for further upscaling and device optimization. The photovoltaic performance results were corroborated with full optical and morphological characterization of the conjugated polymers. We conclude that the determination of the best anchoring position for the side chains is the most rational starting point for the optimization of a polymer with a potential for large-scale fabrication of polymer solar cells.