Dense dual-phase membranes consisting of a molten carbonate embedded in the interconnected pores of a ceramic framework are considered for potential application in CO 2 separation at elevated temperatures utilising ambipolar conduction of carbonate ions and other charge carriers in the molten or solid phase. We have developed an experimental setup for determining transport numbers of various species in the molten carbonate phase by means of electromotive force (emf) measurements. Transport numbers of native and foreign ions are characterized for the eutectic mixture of Li-Na-K carbonate, which is embedded in a porous alumina matrix with Pt or lithiated NiO electrodes. The voltage is measured under activity gradients of CO 2 , O 2 , or H 2 O at 550 • C. Electrochemical impedance spectra are collected during emf measurements. The true transport numbers of both native and foreign ions are calculated by taking into account the electrode polarization. The corrected transport numbers of native (carbonate and alkali metal) ions are close to unity at 550 • C based on the emf under a p C O 2 gradient. Minor transport of oxide ions and hydroxide ions in the molten carbonate is observed under a p O 2 gradient and p H 2 O gradient, respectively. This offers an alternative understanding and operation of molten carbonate dual-phase membranes.Molten carbonates have been characterized with respect to their electrochemical properties and performances in molten carbonate fuel cells (MCFCs). 1-4 Recently, molten carbonates have also been considered together with a mixed electron oxide-ion conducting ceramic in dense dual-phase CO 2 separation membranes. [5][6][7][8][9][10][11][12][13][14][15][16] The principle is to utilize both the transport of carbonate ions in the molten carbonate phase and the transport of oxide ions and/or electrons in the ceramic phase for achieving a high ambipolar transport of CO 2 . Using such dual-phase membranes, it is thus possible to separate CO 2 from a multicomponent gas stream (e.g. that also contains N 2 and/or H 2 ) at high temperature with high selectivity.There are already several reports on the effect of different ceramic phases (alumina, yttria-stabilized zirconia, gadolinia-doped ceria, lanthanum-strontium-cobalt-iron oxide) on the flux of the dualphase membranes, 5,7,8,10,13,14 wherein the influence of the microstructure, the ratio of the two phases, and the wettability of the ceramic surface were investigated. Other publications focused on modelling the above-mentioned properties of such dual-phase membranes in order to investigate the effect of pressure and the presence of oxygen in the flue gas on the surface reaction and bulk conductivity. 11,12,15,17 More recent papers describe the characteristics of thin membranes 18,19 and also the fabrication of asymmetric tubular membranes 9 or hollow fibre membranes. 20 Besides the application in dense membranes, some studies presented the use of ceramic-carbonate nanocomposites as electrolytes in intermediate-temperature solid oxide fuel cells (SO...