In order to fully exploit the green characteristics of solid base catalysts they should be fabricated into macrostructured rather than powder form. Magnesia-rich magnesium aluminate spinel (MgO center dot MgAl2O4) framework catalysts with tunable basicity have been prepared by using gamma-Al2O3 macrospheres (0.5-1.0mm in diameter) as a hard template. The process involves in situ growth of magnesium-aluminum layered double hydroxides (MgAl-LDHs) in the channels of the gamma-Al2O3 macrospheres by the urea hydrolysis method, followed by calcination, tuning of the basicity through etching of excess aluminum with aqueous alkali and a final calcination step. X-ray diffraction (XRD). scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), elemental analysis and low temperature N-2 adsorption-desorption studies demonstrate that the composite MgO center dot MgAl2O4 materials are composed of nanosized rod-like particles aggregated into a spherical framework. Catalytic reactivity was investigated by using methanolysis of soybean oil as probe reaction. The MgO center dot MgAl2O4 composite shows a higher biodiesel yield compared to an MgO/MgAl2O4/gamma-Al2O3 material with the same loading of magnesium prepared by a conventional impregnation method. The enhanced catalytic activity of the former material can be ascribed to its higher basicity, specific surface area, pore volume and pore size. (C) 2008 Elsevier Ltd. All rights reserved.