In the context of increasing global energy demand and greenhouse gas (GHG) emissions, the dry reforming of methane (DRM) to syngas can simultaneously convert CH4 and CO2 into syngas (H2 and CO), which is both environmentally friendly and energy valuable. Carbon deposits and the sintering of active metals often lead to catalyst deactivation. In this work, one-pot microemulsion and impregnation methods have been employed to synthesize Ni@MgAl2O4 and Ni/MgAl2O4 catalysts, respectively, and the effects of different calcination temperatures on the physicochemical properties of the loaded catalysts were investigated. It was shown that Ni@MgAl2O4 exhibited good structural stability and strong metal-support interaction. In addition, the surfaces of Ni@MgAl2O4-800 are rich in adsorbed oxygen species and basic sites, which are favorable for CO2 adsorption and activation and inhibit carbon deposition. In the DRM reaction, the Ni@MgAl2O4-800 catalyst exhibited the highest CH4 and CO2 conversions in the tested temperature range. Its initial conversion of CH4 and CO2 was 92.5 and 93.1%, respectively (800 °C, WHSV = 30,000 mL·gcat-1·h-1). After 20 h of continuous running, the decreases of CH4 and CO2 conversion were <5 and 9%, respectively, and no obvious carbon deposition was observed, which showed good reactivity and anticarbon deposition performance.