An efficient Ni/La0.9Ca0.1AlO2.95 catalyst with low metal content (2.5 wt%) was developed for carbon dioxide (CO2) of methane. The initial CH4 conversion over this catalyst reached 71.4% at 700 °C under atmospheric pressure with a gas hourly space velocity (GHSV) of 48,000 ml/(h gcat), ranking among the highest values in the reported data. Long-term stability test demonstrates that after 20 h of reaction, this catalyst exhibited superior catalytic performance than that with 10.0 wt% of Ni. Structural characterizations reveal that tiny metal size and strong metal-support interactions were two critical structural parameters endowing exceptional reforming performance for this catalyst.