A phenanthrodithiophene (PDT)-difluorobenzoxadiazole (DFBO) copolymer, P-PDT-DFBO, was synthesized and characterized. Replacing a thiadiazole with an oxadiazole ring gives the synthesized polymer a highest occupied molecular orbital (HOMO) about 0.1 V lower, and lowest unoccupied molecular orbital energy levels lower than those of its benzothiadiazole (BT) counterpart, due to the more electron-deficient oxadiazole. Furthermore, since oxadiazole has a larger dipole moment than BT, P-PDT-DFBO exhibits greater aggregation strength than previously reported for P-PDT-DFBT. The low-lying HOMO level of P-PDT-DFBO gave about 0.1 V higher open-circuit voltage (V-oc), yielding over 0.9 V in a fabricated solar cell. From grazing incidence wide-angle X-ray diffraction analysis, P-PDT-DFBO formed a favorable face-on orientation in both neat and blended films, indicating that the incorporation of an oxadiazole moiety can enhance V-oc without any orientation change in the solid state. However, a P-PDT-DFBO-based cell exhibited significantly lower J(sc) and FF, and thus less power conversion efficiency, not >4.43%, due to its lower hole mobility than P-PDT-DFBT. One possible reason for poor performance may be the low crystallinity of P-PDT-DFBO in blended film. This may be caused by its strong aggregation tendency, leading to fast crystallization into a semiamorphous structure or to interference with the construction of long-range ordered structure. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2646-2655