The effect of two different types of polysulfide solvents (i.e., distilled water and methanol) was investigated for zirconium dioxide (ZrO2) based quantum dots sensitized solar cells (QDSSCs). This was mainly depending upon how easily the injection of electrons in the conduction band of CdS particles to the ZrO2 photoanode. Compared to that with methanol solvent-based polysulfide, distilled water-based polysulfide (S2−/Sn2−) electrolytes have efficient electron transportation characteristics at the interface of ZrO2/CdS photoanode and carbon counter electrode. Solar cell efficiency using distilled water-based polysulfide for ZrO2/CdS reaches 1%. The catalytic reaction due to incorporation of polysulfide solvents positively affects the solar cell performance as evident from Nyquist plots. Distilled water-based polysulfide electrolyte has significant impacts on the overall performance of QDSSCs.