Novel three-dimensional (3D) rosette-like carbonate-type Mg-Al layered double hydroxide (MgAl-LDH) hierarchical microstructures were fabricated successfully by a surfactant-assisted coprecipitation method in the presence of hexamethylenetetramine as precipitant, and the morphology-dependent basic catalytic property was exploited. The morphologies of MgAl-LDH aggregates were diversified depending on the synthesis parameters including the type of precipitant, concentration of sodium stearate surfactant, and hydrothermal aging time. Specifically, the morphology of MgAl-LDH particles could change progressively from platelet-like aggregates to rosette-like microspheres with the increasing concentration of sodium stearate. A possible formation mechanism for special 3D flower-like MgAl-LDH microstructures was proposed based on the synergistic effect of precipitant with surfactant. Moreover, the resulting activated rosette-like MgAl-LDH, which was prepared through calcination-rehydration process, showed a higher catalytic activity in the transesterification of tributyrin with methanol, compared with that derived from the conventional platelet-like MgAl-LDH precursor, which was attributed to its higher specific basicity originating from multi-level hierarchical superstructure offering an advantage in contact with more exposed base sites. (C) 2014 Elsevier Inc. All rights reserved.