The effect of catholyte to anolyte amount ratio on the electrodialysis cell performance for HI concentration was investigated. For this purpose, the electrodialysis cell was assembled with Nafion 117 as PEM membrane and activated carbon fiber cloth as electrodes. The initial amount of catholyte was 310 g and that of anolyte varied from 1 to 3 of amount ratio. The calculated electro motive force (EMF) increased with time and the increment enhanced as the amount ratio of catholyte to anolyte decreased. The mole ratios of HI to $H_2O$ (HI molarity) in catholyte were almost the same and exceeded pseudo-azeotropic composition for all amount ratios after 2 h operation. The HI molarity continuously increased with time for 10 h operation. The mole ratio of $I_2$ to HI decreased in catholyte but increased in anolyte. The increment of mole ratio of $I_2$ to HI in anolyte rose as the amount ratio of catholyte to anolyte decreased. In case of 1:1 amount ratio, the cell operation was stopped for the safety at approximately 6 h operation, since the mole ratio of $I_2$ to HI reached solubility limit. The cell voltage of the electrodialysis cell increased with time and the rate of increase was high at low amount ratio. This suggests that the amount ratio of catholyte to anolyte not only crucially influences the cell voltage, but also cell operation condition.