In our early work, KF/ Mg-Al HT [29] had been obtained and successfully used in the transesterification of PO, and the catalyst showed its activity in this reaction with a FAME yield of 85% at optimal condition. Considered that Ca-Al HT had same structure with the Mg-Al HT, while higher alkalescence, in this work, the heterogeneous catalysts KF/ Ca-Al HT were prepared and their catalytic activities were investigated in the transesterification of palm oil with methanol, and at atmospheric pressure the yield of FAME could get over 99%.