Ni-based catalysts supported on alumina derived from the pseudo-boehmite prepared by the impregnation method were employed for catalytic dry reforming of methane reaction at the temperature of 550−750 °C. The effect of calcination temperature on physicochemical properties such as the Ni dispersion, reduction degree, nickel crystallite sizes, and metal−support interaction of the catalysts was investigated. The characterization results show that increasing the catalyst calcination temperature leads to the formation of nickel-alumina spinel, which enhances the metal−support interaction and increases the reduction temperature. The nickel nanoparticle size decreases and the effective dispersion increases with the increasing calcination temperature from 450 °C to 750 °C due to the formation of nickel aluminate. The catalyst calcined at 750 °C exhibits the highest CH4 and CO2 conversion owing to the small Ni0 active sites and high Ni dispersion. In a 200 h stability test in dry reforming of methane at 700 °C, the Ni/Al2O3-750 catalyst exhibits excellent catalytic stability and anti-coking ability.