The efficiency of dye sensitized solar cell depends on the number of factors such as impedance due to anions in the electrolytes, oxidation-reduction process of anions and size of cations of the electrolyte. This paper reports the effect of electrolytes on the photovoltaic performance of hybrid dye sensitized ZnO solar cells based on Eosin Y dye. The size of the cations has been varied by choosing different electrolytes such as LiBr + Br-2, LiI + I-2, tetrapropylammoniurn iodide + I-2 in mixed solvent of acetronitrile and ethylene carbonate. The impedance of anions has been determined by electrochemical impedance spectra. It is observed that Br-/Br-3(-) offers high impedance as compared to I-/I-3(-) couple. The oxidation-reduction reactions of electrolytes are measured by linear sweep voltammogram. It is found that Br-/Br-3(-) is more suitable than an I-/I-3(-) couple in dye sensitized solar cell (DSSC) in terms of higher open-circuit photovoltage production and higher overall energy conversion efficiency. This is attributed to more positive potential of the dye sensitizer than that of Br-/Br-3(-). The gain in V,,c was due to the enlarged energy level difference between the redox potential of the electrolyte and the Fermi level (E-f) of ZnO and the suppressed charge recombination as well. (c) 2006 Elsevier B.V. All rights reserved.