Ni–CaO–ZrO₂ catalysts with different pore structures were prepared and tested for CO₂ reforming of methane. It was found that the catalyst with a mesoporous framework showed both high activity and stability. In particular, no deactivation was observed at a period of run on stream. The characterization confirmed that the “confine effect” of the mesoporous structure prevented Ni particles from sintering during reaction, and as a result, the catalyst with such a mesoporous framework showed a better catalytic performance and resistance to coking.