The oxidation of porous Ni-yttria-stabilized zirconia (YSZ) and Ni-gadolinia-doped ceria (GDC) ceramic-metal (cermet) electrodes in H2O and CO2 atmospheres was studied by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). We show that the oxidation of nickel by the two gases is not similar, as is commonly believed, but it depends on the ceramic type. Nickel is vulnerable to oxidation in H2O but it resists to CO2 in Ni-GDC, as compared to the Ni-YSZ electrode. Inspired by this observation we conceptualize and fabricate Ni-YSZ electrodes modified by ceria nanoparticles, which show significantly higher resistance to CO2 oxidation as compared with conventional Ni-YSZ electrodes. The preparation of tailor-made cermet electrodes with identical bulk/mechanical characteristics but very different surface properties offers a promising fabrication strategy for high-performance and durability solid oxide electrolysis cells for CO2 conversion.