Three n-type polymers, Ppe01, Ppe02, and Ppe03, containing both perylene moieties and fluorine atoms were synthesized. The synthesiszed polymeric perylene derivatives with good compatibility for solution processes were chosen as new acceptor candidates for substitution of C(60) derivatives in poly(3-hexylthiophene)-based organic photovoltaic application, by considering the results based on good thermal stability, high electron affinity ranging from 3.81 to 3.96 eV, absorption property in visible region, and effective photoluminescence quenching in the blend films with P3HT. The potential of the synthesized perylene polymers was investigated by measuring the current-voltage property of the polymeric P3HT: Ppe01 OPV device.