Molecular conformation has a striking function in dominating the molecular orientation, crystallinity, charge mobility, film morphology, and photovoltaic performance for classic donor-pi-acceptor (D-pi-A) type copolymers. Herein, we systematically investigate this correlation by modulating the chemical structures of conjugated polymers composed of a new emerging electron-donating building block of 4,8-bis(4-chlorothiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (BDT-T-Cl). A D-pi-A type copolymer PE31 is synthesized as the reference donor polymer, where BDT-T-Cl, benzotriazole (BTA), and thiophene (T) units are used as the D, A, and bridge, respectively. PE31 realizes a moderate power conversion efficiency (PCE) of 7.62% when paired with a nonfullerene acceptor Y6. The methoxy substitutes in the BTA unit leads to a twisted backbone conformation of the final polymer PE32, which has negative effects on the charge transport and results in a slightly reduced PCE of 7.31%. The intra/interchain noncovalent interactions can be modulated by importing fluorine atoms on the BTA unit (J52-Cl) and further changing the pi-bridge from thiophene to 3-hexylthieno[3,2-b]thiophene (PE4). The backbone of PE4 can be changed to a linear conformation, different from the zigzagged conformation of the other three polymers with thiophene as the pi-bridge. PE4:Y6 shows the highest PCE of 14.02% with the highest fill factor (FF) of 0.75, superior to J52-Cl:Y6 combination (PCE = 12.31% and FF = 0.61). Our results clearly indicate that changing the backbone conformation by pi-bridge engineering has an important significance of achieving the optimal active layer morphology and promising photovoltaic performance.