Membrane capacitive deionization (MCDI) is a simple and low-cost method for brackish water desalination involving reversible electrosorption using high surface area, porous electrodes paired with ion-exchange membranes. Ion-exchange membranes improve charge efficiency and salt adsorption capacity by limiting the transport of co-ions and inhibiting faradaic reactions at the electrode surface. Effective ion-exchange membranes for MCDI should have high permselectivity and low ionic resistance, but there is typically a trade-off between these two properties. In this work, we studied partially sulfonated pentablock copolymer (sPBC) as a cation-exchange coating for MCDI electrodes. sPBC ion exchange coatings of varying ion exchange capacity (IEC, 1.0, 1.5, 2.0 meq g−1) and a range of casting solvent compositions (10–60 wt% n-propanol in toluene) were prepared. Transmission electron microscopy analysis of the membranes showed a morphological change from a micellar to lamellar and then to an inverse micellar structure with increasing polarity of the casting solvent. Water uptake and salt permeability increased with increasing IEC and casting solvent polarity over the entire range of conditions tested. MCDI device studies indicated that charge efficiency and salt adsorption capacity both increased with water uptake over a range of casting solvent compositions due to morphological changes in the sPBC film. This work demonstrates an effective solution-processible ion-exchange layer for MCDI using a self-assembling block copolymer and suggests that ideal ion-exchange coatings for MCDI should have high water uptake to minimize ionic resistance while at the same time maintaining a high charge density of fixed charged groups to achieve high permselectivity.