A novel structural mesoporous alumina (40 mol%)/yttrium doped zirconia nanocrystalline composite has been synthesized by a solvothermal process using ethanol and ethylene glycol as a co-solvent. X-ray diffraction, thermogravimetry/differential scanning calorimetry, Fourier transform infrared, transmission electron microscopy, and nitrogen adsorption are used for the structural characterization. This novel mesoporous alumina/zirconia nanocomposite presents nanocrystalline zirconia particles with a uniform size less than 5 nm surrounded by alumina, forming a kind of core-shell structure after calcined at 800 °C. The mesostructural composite has high surface area (higher than 250 m2/g) and a narrow pore-size distribution of about 3.2 nm throughout the composite sample. The uniformly distributed nanocrystalline zirconia particles and the surrounding wormlike alumina framework act as the inorganic wall for the mesopores.