Three conjugated polymers, in which the electron-donating (D) 5-alkylthiophene-2-yl-substitued benzodithiophene was linked to three different electron-accepting (A) moieties, i.e., benzothiadiazole (BT), diphenylquinoxaline (DPQ), and dibenzophenazine (DBP) derivative via thiophene bridge, were synthesized using the Stille coupling reaction. In particular, the strong electron-withdrawing cyano (CN) group was incorporated into the A units BT, DPQ, and DBP to afford three D–A type target polymers PB–BTCN, PB–DPQCN, and PB–DBPCN, respectively. Owing to the significant contribution of the CN-substituent, these polymers exhibit not only low-lying energy levels of both the highest occupied molecular orbital and the lowest unoccupied molecular orbital, but also reduced bandgaps. Furthermore, to investigate the photovoltaic properties of polymers, inverted-type devices with the structure of ITO/ZnO/Polymer:PC71BM/MoO3/Ag were fabricated and analyzed. All the polymer solar cells based on the three cyano-substituted conjugated polymers showed high open-circuit voltages (Voc) greater than 0.89 V, and the highest power conversion efficiency of 4.59% was obtained from the device based on PB-BtCN with a Voc of 0.93 V, short-circuit current of 7.36 mA cm−2, and fill factor of 67.1%.