Structural and electronic properties of the ground and lowest excited states of the electron-donor conjugated copolymer poly(thieno[3,4-b]thiophene benzodithiophene) (PTB1) are reported based on high-level theoretical investigations. PTB1 combined with phenyl-C61-butyric acid methyl ester (PCBM) results in a bulk heterojunction blend with promising properties for use in organic solar cells. The ab initio algebraic diagrammatic construction method to second order, ADC(2), was used to obtain benchmark data for excited state energies, oscillator strengths, and bond length alternation (BLA) analysis. Time dependent density functional theory (TDDFT) calculations using the exchange-correlation functionals PBE, B3LYP, BHandHLYP, CAM-B3LYP, and LC-wPBE were also performed and compared with ADC(2) calculations. It was shown that a minimum of 20% Hartree-Fock exchange in the functional is necessary to reproduce the major features of the ADC(2) results. Analysis of the BLA results indicates the possibility of exciton trapping by geometry relaxation occurring in the middle of the polymer chain. The corresponding exciton binding energy is about 0.4 eV. Charge distributions in the ground and lowest excited singlet state were analyzed as well. The natural population analysis (NPA) confirms the electronegative character of the benozodithiophene group and the corresponding positive one of the thienothiophene moiety leading to an alternant chain polarization of positive and negative charges. Electron density differences between the S0 and S1 states show a transfer of electron density from double bond regions to areas of single bonds, a feature which parallels nicely the lengthening of double bonds and shortening of single bonds in the S1 state.