A multivariate chemometric approach is proposed for the first time for performance optimization of I-/I-3(-) liquid electrolytes for dye-sensitized solar cells (DSSCs). Over the years the system composed by iodide/ triiodide redox shuttle dissolved in organic solvent has been enriched with the addition of different specific cations and chemical compounds to improve the photoelectrochemical behavior of the cell. However, usually such additives act favorably with respect to some of the cell parameters and negatively to others. Moreover, the combined action of different compounds often yields contradictory results, and from the literature it is not possible to identify an optimal recipe. We report here a systematic work, based on a multivariate experimental design, to statistically and quantitatively evaluate the effect of different additives on the photovoltaic performances of the device. The effect of cation size in iodine salts, the iodine/iodide ratio in the electrolyte and the effect of type and concentration of additives are mutually evaluated by means of a Design of Experiment (DoE) approach. Through this statistical method, the optimization of the overall parameters is demonstrated with a limited number of experimental trials. A 25% improvement on the photovoltaic conversion efficiency compared with that obtained with a commercial electrolyte is demonstrated. (C) 2014 Elsevier B.V. All rights reserved.