The models were established for the theoretical current-voltage characteristics in water dissociation process on a bipolar membrane. Particular attention was given to the transport of the water ions and electrolyte ions as well as the membrane physical structure and configuration. The factors on the water splitting process were adequately analysed based on the derived theoretical current-voltage characteristics and several good suggestions were proposed for decreasing the work voltage in practical operations. In addition, the model can give a reasonable explanation for the catalytic effect of some chemicals, such as amphiprotic hydroxide compounds, weak polymeric acids and bases, etc. It is shown that the catalyst may be responsible for the increase in dissociation rate constant of water and therefore enhance the water dissociation. The guidelines for choosing a proper catalyst were also proposed.