Four pyrene–porphyrins were synthesized to study the isomer effect on the photovoltaic performance of dye-sensitized solar cells. One of these porphyrins is conjugated with a terminal pyrene, whereas the other three are each attached with a pyrene bearing an extra donor group. According to the positions of the extra donor and porphyrin core on pyrene, the 1,6-, 1,8-, and 2,7-isomers were compared for their fundamental and photovoltaic properties. For fundamental properties, UV–visible absorption, fluorescence emission, electrochemistry, and DFT calculations were carried out. For photovoltaic measurements, the seemingly inferior 1,8-isomer outperforms others with an overall efficiency of 10.30% under one-sun irradiation. Superior photovoltaic performance of the 1,8-isomeric dye may be related to the so-called umbrella effect. The findings of this work may provide insight into isomeric dye design for future applications.