Dry reformation of methane (DRM) is an attractive route to utilize greenhouse gases, which has significant environmental and economic benefits. Ni-based catalysts are one of the most important catalysts in DRM. However, their deactivation induced by sintering and coking remains a major challenge. In this work, a series of metakaolinite-supported Ni catalysts (Ni/MK) with varying content of unsaturated coordinated aluminum were prepared. It was found that the catalytic stability could be improved by controlling the unsaturated coordinated aluminum content. Ni/MK-800, with the highest unsaturated coordinated aluminum content, demonstrated at least 18 times enhanced stability duration compared with Ni/MK-600 with the lowest content. The increasing content of unsaturated coordinated aluminum enhanced the metal-support interaction, which subsequently improved the anti-sintering and anti-coking performance and thus improved the catalytic stability. This work provided an optional strategy for designing highly stable DRM catalysts by controlling the coordinative unsaturation degree of central ions in support.