Abstract: A Ni–Cr anode, dip coated with Ce oxide for increasing the resistance to sulfur poisoning of high-temperature molten carbonate fuel cell, has been investigated by neutron diffraction. Crystallographic characterization of the phases present in this anode has been obtained by Rietveld refinement. In the substrate Ni–Cr is detected, with (Formula presented.) structure and weight volume fraction of 68.50(46) wt %. Additionally, due to oxidation during coating also NiO is present (space group (Formula presented.)), with weight volume fraction of 25.28(18) wt %. The thin protective layer consists of nanostructured CeO2 ((Formula presented.)), with an estimated massive volume fraction of 6.3(5) wt %. These results support the effectiveness of the adopted CeO2 deposition procedure and show the usefulness of neutron diffraction also for investigating thin protective layers.