We report a novel combination of organic sensitizer and redox mediator in the electrolyte for dye-sensitized solar cells (DSSCs): a thiophene dye and nitroxide radicals. Nitroxide radicals and their oxidized counterparts of oxoammonium cations show robust reversible redox reactions, thus supporting robust DSSC operations. Moreover, their redox potentials (E 1/2) and thus open-circuit voltages (V OC) can be tuned further by attached functional groups. Optical and electrochemical characterization reveal that these new combinations exhibit enhanced V OC and power conversion efficiencies compared to the existing iodine mediator (I⁻/I⁻3) due to the increased V OC. Also, the selection of the sensitizer–redox mediator turns out to be critical in the overall cell performance. Indeed, the typical ruthenium dye loses its light absorption capability when it is operated in conjunction with the nitroxide radicals.