Structured composite Ni(Clx)/CeO2/η-Al2O3/FeCrAl catalysts are developed for the reaction of preferential methanation of carbon monoxide in the presence of carbon dioxide. The use of a FeCrAl alloy wire mesh as a support for Ni(Cl)/CeO2 allows preparation of a heat-conducting catalyst that is similar in performance and physical-chemical properties to the highly efficient catalysts in the form of micro pellets, as confirmed by catalytic tests and XRD, XPS, TEM, SEM, EDX characterization techniques. Catalytic tests are carried out in hydrogen-rich mixture which contains (vol. %): 1 CO, 65 H2, 10 H2O, 20 CO2, He – balance; weight hourly space velocity is 29,000 cm3gcat −1h−1. The structured catalyst with highly dispersed nickel and optimal chlorine content provides CO removal to a level of <10 ppm in the temperature interval of 230–300 °C. XRD, TEM, SEM and EDX analysis confirm the presence of Ni nanoparticles and CeOCl species in the catalytic coating. XPS study of samples after reductive pretreatment (simulating CO preferential methanation reaction conditions) in the preparation chamber of the spectrometer reveals the metallic state of Ni and high concentrations of Cl and Ce3+ on the catalyst surface.