The KF/hydrotalcite (HT) solid base catalysts were prepared by impregnation and characterized by X-ray diffraction. Biodiesel can be obtained from transesterification of palm oil with methanol over the KF/HT catalysts. The effect factors, such as KF/HT load ratio, methanol/oil molar ratio, catalyst amount, reaction time, and reaction temperature, were investigated. When the reaction was carried out at 338 K, with palm oil/methanol molar ratio of 12: 1, reaction time of 3 h, and catalyst amount of 3 wt %, the yield of fatty acid methyl esters can reach 85%, and when the reaction time prolonged to 5 h, the yield can become 92%.