Porous ceria: 20 mol% gadolinia (20GDC) ceramic membranes were prepared by tape casting (TC) and freeze-drying (FD) techniques, obtaining ceramic matrices with randomly dispersed round pores and with an aligned pore structure, respectively. Samples were sintered at 1450 ??C, followed by infiltration of molten eutectic sodium-lithium carbonates (NLC). The pore morphology of 20GDC-TC and 20GDC-FD composite membranes was evaluated by analysis of scanning electron microscopy images. The electrical resistivity was determined by electrochemical impedance spectroscopy in the 1 Hz - 10 MHz frequency range from 300 ??C to 700 ??C, covering the solid-to-molten NLC temperature range, showing that the aligned pore structure improved the conductivity of the ceramic matrix in addition to facilitating molten carbonate infiltration, improving the total (bulk + interfaces) electrical conductivity of the composite membrane. Permeation experiments showed high CO2 permeation rates reached 5.35 ?? 10???7 mol m???2 s???1 Pa???1 at 800 ??C. The infiltration of molten sodium-lithium carbonate in gadolinium-doped ceria prepared by the freeze-drying technique is proposed as an optimized procedure for producing membranes for carbon dioxide separation.Funda????o de Amparo ?? Pesquisa do Estado de S??o Paulo (FAPESP)Conselho Nacional de Desenvolvimento Cient??fico e Tecnol??gico (CNPq)FAPESP: 17/11937-4; 13/07296-2CNPq: 302357/2018-1; 305889/2018-4; 305620/2019-3