The effect of additives in the synthesis of biodiesel fuel using supercritical methanol was studied in order to examine the possibility of application of spent vegetable oil as a raw material, which has high contents of water or free fatty acid. The experiments were performed by varying the contents of water, free fatty acid or antioxidants respectively in a batch reactor. The contents of fatty acid methyl ester was analyzed by a gas chromatography. As the water contents increased, the contents of fatty acid methyl ester decreased, however, the decrease was very little compared with the alkaline and acid catalyst. The effect of the contents of free fatty acid, vitamin E, and β-carotene was negligible.