Highly-dispersed Ni-NiO nanoparticles was successfully anchored on an SiO2 support via a one-pot synthesis and used as heterogeneous catalysts for CO methanation. The as-obtained Ni-NiO/SiO2 catalyst possessed a high Ni content of 87.8 wt.% and exhibited a large specific surface area of 71 m2g−1 with a main pore diameter of 16.7 nm. Compared with an H2-reduced Ni-NiO/SiO2 (i.e., Ni/SiO2) catalyst, the Ni-NiO/SiO2 displayed a superior CO methanation performance. At the temperature of 350 °C, the Ni-NiO/SiO2 showed a CO conversion of 97.1% and CH4 selectivity of 81.9%, which are much better values than those of Ni/SiO2. After a 50-h stability test, the Ni-NiO/SiO2 catalyst still had an overwhelming stability retention of 97.2%, which was superior to the 72.8% value of the Ni/SiO2 catalyst.