Five new copolymers based on the anthanthrone moiety were synthesized using Stile coupling. The anthanthrone unit was coupled with two electron-rich units (thiophene and carbazole) and three electron-poor units (thienopyrroledione, diketopyrrolopyrrole, and benzothiadiazole). The optoelectronics properties of the polymers were investigated and suggest that the anthanthrone moiety dictates the electronic properties of the materials with little regards to the nature of the comonomers. Fluoride-promoted photoinduced electron transfer on anthanthrone derivatives yielded to radical anion species that can be reversibly oxidized to the neutral form by exposure to air.