The effect of using a binary iodide salt mixture in N719 dye-sensitized TiO2 solar cells (DSSCs) is investigated. The cells use tetrapropylammonium iodide (Pr4NI) and magnesium iodide (MgI2) in a plasticized polyacrylonitrile gel in glass/FTO/nano-porous TiO2/gel, I2/Pt/FTO/glass solar cell structure. The salt composition in the gel electrolyte is varied to optimize the efficiency of DSSCs. The DSSCs with MgI2 or Pr4NI as the only iodide salt showed the efficiencies 2.56 and 4.16 %, respectively, under AM 1.5 (100 mW cm−2) illumination while the DSSC with mixed cations with 18.4:81.6 MgI2:Pr4NI molar ratio shows the highest efficiency of 5.18 %. Thus the efficiency enhancement, relative to the high efficiency end member is about 25 %. DC polarization measurements establish the predominantly ionic behavior of the electrolytes, and show that the variation of efficiency with salt composition correlates with the change in short circuit photocurrent density (Jsc), which appears to be governed by the iodide ion conductivity. It is also found that Jsc correlates with the iodide ion transference number estimated from DC polarization data taken with non-blocking iodine electrodes. This study suggests that binary iodide mixtures may be used to obtain efficiency enhancement in different types of DSSCs based on polymeric, gel, or solvent electrolytes.