Regioregular (P1) and random (P2) polymers were prepared by the reaction of equimolar amounts of dibromides M2 or M3 with bis(stannyl) monomer M1. The regioregularity of the conjugated chain in P1 was shown to affect considerably its optical properties. The HOMO/LUMO values and electrochemical band gap for polymers P1 or P2 found by cyclic voltammetry are–5.40/–3.40,–5.31/–3.33, and 2.00/1.96 eV, respectively. The LUMO levels for P1 and P2 are located higher than for PC71BM (–4.3 eV) by 0.84 and 0.97 eV, respectively. The low-lying HOMO levels of P1 and P2 are favorable for the high value of open-circuit voltage and make these polymers attractable candidates for polymer solar cells.