Abstract: The supported solid base catalyst Na₂O/Al₂O₃-MgO, was prepared through ammonia precipitation process, impregnation process with Na₂CO₃ and calcination process. The effects of various process condition on the methyl esterification yield of Malania oleifera oil were analyzed by applying Na₂O/Al₂O₃-MgO catalyst. The findings indicated that by the analyses of XRD, SEM and BET, it could be seen that catalyst precursor had the structure of hydrotalcite-like compounds and the specific surface area of roasted catalyst was 29.5 m²/g. In addition to Al₂O₃ and MgO, Na-Al and Na-Al-Mg oxides were identified in the catalyst by XRD. By single factor test and orthogonal test, considering higher conversion rate and lower production cost, the optimal process condition for applying the Na₂O/Al₂O₃-MgO catalyst in methyl esterification of M.oleifera oil was obtained. In the condition of keeping the reflux of methanol, the catalyst amount as 2% and the molar ratio of methanol to oil as 15:1, after a reaction time of 5 h, the conversion rate of methyl esterification of M.oleifera oil could achieve 96.4%.