In this paper theoretical and experimental results for water softening by bipolar membranes in the presence of polyelectrolytes have been presented. A modified capillary model is introduced for flow of a multiion solution through the membrane. The most important modifications are: an integral boundary condition in Poisson equation and a coupling coefficient in the convective molar flux by using the modified Faxen equation. In addition, electrical permittivity of solution has not been considered as a constant. The predictions of the model were compared well with the experimental data obtained by using bipolar membranes in a recirculating test system in the presence of polyelectrolytes.