Two kinds of thieno[3,4-b]pyrazine-based monomers, 2,3-dimethyl-5,7-di(2-bromothien-5-yl)-thieno[3,4-b]pyrazine and 2,3-dipheliyl-5,7-di(2-bromothien-5-yl)-thietlo[3,4-b]pyrazine, were synthesized via an improved synthetic route. These two monomers and 4,7-di(2-brothothien-5-yl)-2,1,3-benzothiadiazole were copolymerized with three donor segments (fluorene, carbazole, and indolocarbazole) separately by a Suzuki cross-coupling reaction to give six types of 5,7-dithien-2-yl-thieno[3,4-h]pyrazine (DTTP)-based donor-acceptor (D-A) copolymers (TPI-6) and three types of 5,7-dithien-2-yl-2,1,3-benzitguaduazole (DTBT)-based D-A copolymers (PF-DTBT, PC-DTBT, and PIC-DTBT). The optical properties, electrochemical behavior, and energy levels of these nine copolymers were investigated. The photovoltaic performance of the copolymers was compared and discussed considering their energy levels.