A series of conjugated donor (D)-pi-acceptor (A) copolymers, P(BDT-F-BT), P(BDT-T-BT), and P(BDT-TT-BT), based on benzodithiophene (BDT) donor unit and benzothiadiazole (BT) acceptor unit with different pi-bridges, were designed and synthesized via a Pd-catalyzed Stille-coupling method. The pi-bridges between the BDT donor unit and BT acceptor unit are furan (F) in P(BDT-F-BT), thiophene (T) in P(BDT-T-BT) and thieno[3,2-b]thiophene (TT) in P(BDT-TT-BT). It was found that the pi-bridges significantly affect the molecular architecture and optoelectronic properties of the copolymers. With the pi-bridge varied from furan to thiophene, then to thieno[3,2-b]thiophene, the shape of the molecular chains changed from z-shaped almost straight line gradually. Band gaps of P(BDT-F-BT), P(BDT-T-BT) and P(BDT-TT-BT) were tuned from 1.96 to 1.82 to 1.78 eV with HOMO levels up-shifted from -5.44 to -5.35 to -5.21 eV, respectively. Bulk heterojunction solar cells with the polymers as donor and PC71BM as acceptor demonstrated power conversion efficiency varied from 2.81% for P(BDT-F-BT) to 3.72% for P(BDT-T-BT) and to 4.93% for P(BDT-TT-BT). Compared to furan and thiophene, thieno[3,2-b]thiophene pi-bridge in the copolymers shows superior photovoltaic performance. The results indicate that the photovoltaic performance of some high efficiency D-A copolymers reported in literatures could be improved further by inserting suitable pi-bridges.