Synthesis strategy of hierarchical aluminosilicates was carried out by varying the starting material, type of a basic solution, and the hydrothermal condition. Aluminosilicate was synthesized using pre-treated low-quality kaolin by three kinds of basic solution, such as sodium hydroxide, sodium fluoride, and tetrapropyl ammonium hydroxide. The hydrothermal condition was carried out by gradual temperature and constant temperature. The desired mole ratio of Si/Al achieved by dealumination or by addition of silica. Products were characterized by X-ray diffraction, FTIR spectrometry, and nitrogen physisorption. Cation exchange was carried out on the product to obtain an acid catalyst. The acidity test of the catalyst was carried out by FTIR-pyridine spectrometry. The catalyst activity test was carried out to the acetalization reaction of 3,4-dimethoxybenzaldehyde with propylene glycol. The results showed that the catalyst synthesized with the basic solution of tetrapropyl ammonium hydroxide had the highest acid site number and the highest conversion of 3,4- dimethoxybenzaldehyde to acetal.