We have used the quartz crystal microbalance with dissipation monitoring (QCM-D) technique to investigate how mono- and divalent cations influence the formation Of Supported (phospho)lipid bilayers (SPB, SLB). occurring via deposition of nanosized palmitoyloleoyl phosphatidylcholine (POPC) vesicles on a SiO2 support. This process is known to proceed Via initial adsorption of intact vesicles until a critical surface coverage is reached. where the combination of vesicle-surface and vesicle-vesicle interaction Causes the vesicles to rupture. New vesicles then rupture and the lipid fragments Fuse until a final continuous bilayer is formed. We have explored how this process and the critical coverage are influenced by different mono- and divalent ions and ion concentrations, keeping the anions the same throughout the experiments. The same qualitative kinetics is observed for all cations. However, different ions cause quite different quantitative kinetics. When compared with monovalent ions, even very small added concentrations of divalent cations cause a strong reduction of the critical coverage, where conversion of intact, adsorbed vesicles to bilayer Occurs. This bilayer promoting effect increases in the order Sr2+ < Ca2+ < Mg2+. Monovalent cations exhibit a much weaker but similar effect in the order Li+ > Na+ > K+. The results are of practical value for preparation of lipid bilayers and help shed light on the role of ions and on electrostatic effects at membrane surfaces/interfaces.