This work is concentrated on elucidating the mechanism of the electric field enhanced water dissociation. A simple model was established for the theoretical current-voltage characteristics in water dissociation process on a bipolar membrane based on the existence of a depletion layer and Onsager's theory. Particular attention was given to the influence of applied voltage on depletion thickness and the dissociation constant. The factors on the water splitting process, such as water diffusivity, water content, ion exchange capacity, temperature, relative permittivity, etc. were adequately analysed based on the derived model equations and several suggestions were proposed for decreasing the applied voltage in practical operation. The water dissociation tests were conducted and compared with both the theoretical calculation and the measured current-voltage curves reported in the literature, which showed a very good prediction to practical current-voltage behavior of a bipolar membrane at high current densities when the splitting of water actually commenced.