Dye-sensitized solar cells (DSCs) are considered to be a promising alternative to Si-based photovoltaic cells. The electrolyte of the DSC primarily uses triiodide/iodide (I3−/I−) as a redox couple. Therefore, it is essential to understand the regeneration and recombination kinetics of the I3−/I− redox couples in the device. In this context, controlling the total and local concentrations of the I3−/I− redox couples is an important parameter that can influence the DSC performance. Here, we propose that the introduction of a sodium bis (2-ethylhexyl) sulfosuccinate (AOT)/water system to the I3−/I− electrolyte enables the control of the concentration of the redox couples, which consequently achieves a high power conversion efficiency of ∼11% for ∼1000 h (under 1 sun illumination) owing to the enhanced dye-regeneration efficiency and the reduced recombination rate. This novel concept assists in the comprehension of the regeneration and recombination kinetics and develops highly efficient DSCs.