The influence of co-ion leakage through a bipolar membrane on both I-V response and current efficiency of water dissociation was studied. The monofilm bipolar membrane was synthetized from a pretreated ETFE film functionalized by quaternized ammonium groups on one side and sulphonic groups on the other. The co-ion leakage of this bipolar membrane immersed in NaCl solutions was measured by means of radiotracers. The results showed that the greater the co-ion leakage, the lower was the current efficiency of water dissociation. A theoretical analysis of ion transfer through the bipolar membrane pointing out the effect of boundary layer on the limiting leakage current is presented.