Single metal ion-phospholipid complexes are observed in biphasic electrospray ionization mass spectrometry (BESI-MS) using a dual-channel microsprayer. Such a microsprayer makes it possible to put into contact two immiscible liquids within the Taylor cone. Thus, L-alpha-dipalmitoyl phosphatidylcholine (DPPC) dissolved in 1,2-dichloroethane (DCE) reacts with aqueous metal cations (M = Na+, K+, Ca2+, Cu2+, La3+) yielding the formation of [M-DPPCn](z+) complexes. The number of phospholipid molecules ranges from 1 to 4 for monovalent ions, to 8 for divalent and to more than 10 for trivalent ions respectively. The large number of ligands observed involves the formation of solvent free single ion-phospholipid complexes.