Catalysts of Ni supported on home-made mesoporous alumina (Ni/M-Al₂O₃) were prepared via facile incipient impregnation method and calcined under different temperature (500–800 °C). Compared with catalysts of Ni supported on commercial alumina, they showed much higher conversion and lower carbon deposition in methane dry reforming (DRM). Among the catalysts, Ni/M-Al₂O₃-700 exhibited the highest DRM activity, with 77.6% CH₄ conversion and 85.4% CO₂ conversion at 700 °C. TPR revealed that almost all the Ni was in the form of NiAl₂O₄ spinel after calcination at 700 °C. Due to the strong metal-support interaction of NiAl₂O₄ structure, the Ni crystal size of Ni/M-Al₂O₃-700 after reduction was around 5 nm. TGA and TEM results showed its carbon deposition after 20 h DRM test was only 3.8% and mainly in the form of amorphous carbon. This work indicates that the formation of NiAl₂O₄ spinel is beneficial to activity and stability towards DRM reaction and controlling calcination temperature is crucial.