The performance of dye sensitized nanocrystalline TiO2 solar cells based on quasi-solid state PAN electrolytes containing a series of six quaternary ammonium iodide salts NH4I, Eth(4)NI, Prop(4)NI, But(4)NI, Pent(4)NI, Hex(4)NI with different cation sizes has been evaluated. Even though the total ionic conductivity decreases with increasing cation size from NH4I to Hex(4)NI, the iodide ion conductivity in the electrolytes increases with cation size. The open circuit photovoltage (V-oc) of the dye sensitized solar cells also increases with cation radius. The efficiency of the DSSCs varies with cation size and exhibits a maximum for Prop(4)NI salt. The short circuit photo current density (J(sc)) follows a similar variation with cation size, suggesting a strong correlation between the cation size dependence of efficiency and J(sc). The DSSC fabricated with tetrapropylammonium iodide exhibited the maximum efficiency of 4.30% with maximum J(sc) of 10.78 mA cm(-2) and a V-oc of 0.746 V. The results have been interpreted on the basis of "the electrolyte effects" where J(sc) is determined essentially by the iodide ion conductivity and "the electrode effects" where the J(sc) and V-oc are determined by the cation adsorption in the dyed TiO2 electrode and resulting electron dynamics at the semiconductor/electrolyte interface. For DSSCs with small cations, electrolyte effects appear to be dominating and rate determining while for DSSCs with larger cations, electrode effects appear to be dominating and rate determining. (C) 2013 Elsevier Ltd. All rights reserved.