Two medium-bandgap polymers composed of benzo[1,2-b:4,5-b′]dithiohpene and 2,1,3-benzothiadiazole with 6-octyl-thieno[3,2-b]thiophene as a π-bridge unit are synthesized and their photovoltaic properties are analyzed. The two polymers have deep highest occupied molecular orbital energy levels, high crystallinity, optimal bulk-heterojunction morphology, and efficient charge transport, resulting in a power conversion efficiency of as high as 9.44% for a single-junction polymer solar-cell device. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.