A series of ordered mesoporous Ni-Fe-Al ternary oxide composites were prepared via a one-pot evaporation-induced self-assembly (EISA) method and applied in a CO methanation reaction to produce synthetic natural gas. The results showed that the ordered mesoporous Ni-Fe-Al catalyst with proper amount of Fe species (10N1FOMA) had better both CO conversion and CH4 selectivity than the impregnation-derived 10N1FA catalyst with unordered mesopores and identical component, owing to the higher Ni dispersion and larger H-2 uptake. In a 120 h atmospheric-pressure lifetime test, the ordered mesoporous 10N1FOMA catalyst showed significant enhancement in both antisintering and anticoking properties in comparison with the unordered mesoporous 10N1FA, mainly because of the confinement effect of the mesopore channels, the weak acidity of ordered mesoporous alumina support, and the smaller Ni particle size (<5.0 nm).