In an effort to determine the role that monovalent ions play in the modification of intermembrane forces, we have measured these forces between charged phospholipid bilayers in monovalent ionic solutions. The osmotic stress technique allowed the net electrostatic pressure between the bilayers to be measured while their separation was concurrently determined by x-ray diffraction. Taken together, these measurements yielded electrostatic pressure as a function of bilayer separation. We have related measured pressures to the bilayer surface charge density and surface potential through an exact solution of the full nonlinear Poisson-Boltzmann equation for this system. Quantitative differences in bilayer separation amongst monovalent alkali metal cations indicated differential binding of these to phosphatidylglycerol (PG), phosphatidylserine (PS), and phosphatidic acid (PA); binding affinity series were determined for Li+, Na+, K+, Cs+, and TMA+ ions to these lipids. The anions Cl-, Br-, I-, and CH3COO- were found to have no differential effect on the repulsive forces between PS bilayers. Debye lengths for the electric double layer estimated from the slopes of the experimental pressure curves were consistently longer than predicted on the basis of classic Gouy-Chapman theory. Estimates of the van der Waals Hamaker coefficient between bilayers of PS and PG in salt solution were found to be weaker than between phosphatidylcholine bilayers in pure water, a difference possibly due to electromagnetic retardation and ionic screening.