The phase behavior of ion-containing block copolymer membranes in equilibrium with humidified air is studied as a function of the relative humidity (RH) of the surrounding air, ion content of the copolymer, and temperature. Increasing RH at constant temperature results in both disorder-to-order and order-to-order transitions. In-situ small-angle neutron scattering experiments on the open block copolymer system, when combined with wafer uptake measurement, indicate that the disorder-to-order transition is driven by an increase in the partial molar entropy of the water molecules in the ordered phase relative to that in the disordered phase. This is in contrast to most systems wherein increasing entropy results in stabilization of the disordered phase.