The electron donor poly-thienothiophene-benzodithiophene (PTB) polymer series displays remarkable properties that lead to more efficient bulk heterojunction (BHJ) organic solar cells. In this work, the ground and four excited states (bright S1 and dark S2-S4) of three different members of the PTBn (n = 1, 6, 7) series were studied and compared with the prototypical poly(3-hexylthiophene) (P3HT) donor polymer. Time-dependent density functional theory was employed to investigate oligomers of similar sizes (∼50 Å). Charge alternation electron accumulation and depletion regions of the four transitions are concentrated on the inner units, thereby favoring interaction with the electron acceptor in a BHJ. The bright S1 transition energies of PTBn are about 0.2 eV lower as compared to P3HT, thereby allowing a better match of their levels with the typical C60-type acceptor moiety in a BHJ. Side chains play a minor role in the electronic spectrum (less than ∼0.1 eV). The most efficient PTB7 transfers more electronic charge from its electron-rich benzodithiophene subunit to its electron-deficient thieno[3,4-b] thiophene subunit as compared to PTB1 and PTB6. We show that the dipolar effect, a partial concentration of negative and positive charges on the different parts of the donor polymer that favors charge separation, is more pronounced in PTBn polymers and typically an order of magnitude larger as compared to P3HT. These effects are conspicuous for the most efficient polymer of the series, PTB7, with its fluorine substituent shown to play a crucial role.