Here, we compare analogous cyclic and acyclic pi-conjugated molecules as n-type electronic materials and find that the cyclic molecules have numerous benefits in organic photovoltaics. This is the first report of such a direct comparison. We designed two conjugated cycles for this study. Each comprises four subunits: one combines four electron-accepting, redox-active, diphenyl-perylenediimide subunits, and the other alternates two electron-donating bithiophene units with two diphenyl-perylenediimide units. We compare the macrocycles to acyclic versions of these molecules and find that, relative to the acyclic analogs, the conjugated macrocycles have bathochromically shifted UV-vis absorbances and are more cathode-easily reduced. In blended films, macrocycle-based devices show higher electron mobility and good morphology. All of these factors contribute to the more conversion efficiency observed in organic photovoltaic devices with these macrocycles as the n-type, electron transporting material. This study highlights the importance of geometric design in creating new molecular semiconductors. The ease-with which we can design and tune the electronic properties of these cyclic structures charts a dear path to creating a new family of cyclic, conjugated molecules as electron transporting materials in optoelectronic and electronic devices.