A series of medium bandgap polymers based on 9,10‐thienylanthracene and benzothiadiazole are synthesized. The optical, electrochemical, intermolecular, and charge transport characteristics of the polymers are tuned by the introduction of various substituents. The fluorine‐substituted polymer exhibits much enhanced charge generation with reduced bimolecular recombination, thereby achieving a high power conversion efficiency exceeding 8%.