Biphasic electrospray ionization (BESI) mass spectrometry is achieved by using a dual-channel microsprayer, where channels filled with different immiscible phases meet at the Taylor cone. Two types of interfacial complexation reactions have been studied: the interfacial complexation of aqueous lead ions by thioether crown molecules, and the interfacial complexation of an aqueous dipeptide by dibenzo-18-crown-6 as ionophore. The mass spectra also give valuable information on the stoichiometry of the complexation reaction.