An Al2O3-coated SiC, Al2O3@SiC, was designed via the evaporation-induced self-assembly method to serve as a composite support for Ni catalysts in synthetic natural gas (SNG) production through carbon monoxide (CO) methanation. Scanning electron microscopy images of the Al2O3@SiC composite showed that the SiC surface was coated by an Al2O3 layer homogeneously. The Ni/Al2O3@SiC catalyst exhibited excellent initial activity and superior long-term stability in CO methanation. The structural characterizations revealed that the high activity of the Ni/Al2O3@SiC catalyst was mainly due to the small size of Ni nanoparticles and the mesoporous structure of Al2O3 layers coated on SiC surface. The superior stability of the Ni/Al2O3@SiC catalyst was rationalized by the enhanced anticoke and antisintering properties. The present work will provide guidelines in the synthesis of highly efficient composite catalysts for SNG production.