Supported lipid bilayers (SLBs) are a useful tool for studying the interactions between lipids and other biomolecules that make up a cell membrane. SLBs are typically formed by the adsorption and rupture of vesicles from solution. Although it is known that many experimental factors can affect whether SLB formation is successful, there is no comprehensive understanding of the mechanism. In this work, we have used a quartz crystal microbalance (QCM) to investigate the role of the salt in the buffer on the formation of phosphatidylcholine SLBs on a silicon dioxide (SiO2) surface. We varied the concentration of sodium chloride in the buffer, from 5 to 150 mM, to find the minimum concentration of NaCl that was required for the successful formation of an SLB. We then repeated the experiments with other group I chloride salts (LiCl, KCl, and CsCl) and found that at higher salt concentrations (150 mM) SLB formation was successful for all of the salts used, and the degree of deformation of the adsorbed vesicles at the critical vesicle coverage was cation-dependent. The results showed that at an intermediate salt concentration (50 mM) the critical vesicle coverage was cation-dependent and at low salt concentrations (12.5 mM) the cation used determined whether SLB formation was successful. We found that the successful formation of SLBs could occur at lower electrolyte concentrations for KCl and CsCl than it did for NaCl. To understand these results, we calculated the magnitude of the vesicle-surface interaction energy using the Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended-DLVO theory. We managed to explain the results obtained at higher salt concentrations by including cation-dependent surface potentials in the calculations and at lower salt concentrations by the addition of a cation-dependent hydration force. These results showed that the way that different cations in solution affect the 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC)-SiO2 surface interaction energy depends on the ionic strength of the solution.