Polysulfide electrolyte is the most commonly utilized electrolyte in quantum dot-sensitized solar cells (QDSSCs). Recently, however, a redshift in the relative positions of the absorbance and incident photon conversion efficiencies of CdSe QDs in polysulfide solutions has been reported. We conduct extensive analyses of CdSe QD films comparing those exposed to polysulfide solution with unexposed films; indeed, a redshift in the absorbance is observed after exposure. Most strikingly, we observe that a photocurrent response from films immersed in sodium sulphite is observed only after exposure to polysulfide solution. We demonstrate this is due to a combination of both QD ripening and a change in the QD capping layer. The results demonstrate that a polysulfide processing step significantly alters the photoelectrochemical performance of QDs.