A twisted bay-substituted tetraphenyl functionalized perylenediimide monomer (TP-PDI) is synthesized. A high power conversion efficiency of 4.1% is achieved for organic solar cells incorporated a combination of TP-PDI electron acceptor and PTB7-Th electron donor, indicating that chemical modification of PDI monomers is a useful way of designing high-performance non-fullerene electron acceptors. 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.