In this work, the block-shaped Al-based metal-organic frameworks (Al-MOFs) MIL-53 have been synthesized by hydrothermal method. To detect the correlation between the structure of Al-MOFs and the formation of alumina, the ligands are eliminated by thermal treatment. MIL-53 and the calcination products were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), nitrogen adsorption-desorption and solid-state Al-27 nuclear magnetic resonance (Al-27 NMR). It was found that after calcination, the block-shaped Al-MOFs precursor turns into high-crystallinity mesoporous alumina nanosheets, and the thermal treatment product gamma-alumina possesses a dual pore system and a large surface area (146 m(2)/g), with five-fold aluminum. During the thermal treatment process, the structure of MIL-53 and its secondary building units have structure-directed effect in the formation of alumina. (C) 2015 Elsevier Ltd. All rights reserved.