This investigation demonstrates the feasibility to fabricate high quality ceramic–carbonatemembranes based on mixed-conducting ceramics. Specifically, it is reported the simultaneous CO2/O2permeation and stability properties of membranes constituted by a combination of ceramic and carbonate phases, wherein the microstructure of the ceramic part is composed, in t, of a mixture of fluorite and perovskite phases. These ceramics showed ionic and electronic conduction, and at the operation temperature, the carbonate phase of the membranes is in liquid state, which allows thetransport of CO32– and O2– species via different mechanisms. To fabricate the membranes, the ceramicpowders were uniaxially pressed in a disk shape. Then, an incipient sintering treatment was carried out in such a way that a highly porous ceramic was obtained. Afterwards, the piece is densified by the infiltration of molten carbonate. Characterization of the membranes was accomplished by SEM, XRD, and gas permeation techniques among others. Thermal and chemical stability under an atmosphere rich in CO2 was evaluated. CO2/O2 permeation and long-term stability measurements were conductedbetween 850 and 940 ℃. The best permeation–separation performance of membranes of about 1 mm thickness, showed amaximum permeance flux of about 4.46×10–7 mol·m–2·s–1·Pa–1 for CO2 and 2.18×10–7 mol·m–2·s–1·Pa–1for O2 at 940 ℃. Membranes exhibited separation factor values of 150–991 and 49–511 for CO2/N2and O2/N2 respectively in the studied temperature range. Despite long-term stability test showedcertain microstructural changes in the membranes, no significant detriment on the permeation properties was observed along 100 h of continuous operation.