Catalysts based on CaO/MgAl oxides were prepared by Ca(NO3)(2)center dot 4H(2)O impregnation onto MgAl hydrotalcite followed by calcination at 600 degrees C/0.5 h. The materials were characterized by means of XRD, N-2 physisorption, FEG-SEM equipped with energy-dispersive X-ray spectroscopy (EDS) and TPD of CO2. The oxide reactivities were evaluated using the model transesterification reaction between methyl acetate and ethanol under mild reaction conditions (50 degrees C, ethanol/methyl acetate molar ratio = 6/1 and 4 wt%of catalyst). MgAl mixed oxide was inactive for transesterification. On the other hand, the Ca addition onto the oxides considerably increased the base site amounts and strengths of the Ca/MgAl, greatly improving their catalytic performances. Remarkably high conversions were obtained for 40-Ca/MgAl compared to commercial CaO. Thus, the CaO dispersion over MgAl mixed oxide showed to significantly improve the catalytic performance of CaO. Stability tests revealed that the Ca/MgAl can be reused for at least 5 reaction cycles and the reaction occurs through a heterogeneous process. Due to the high activity, this type of catalyst can be pointed as a promising heterogeneous catalyst for biodiesel production although the Ca leaching must be formerly resolved for practical use. (C) 2014 Elsevier B.V. All rights reserved.