The methods for preparation of pillared materials with ZrO2, TiO2, or SiO2 in the interlayer of layered perovskite structural oxides, HLaNb2O7 (HLa), were examined in detail. HLa that had been intercalated with n-amines of different carbon chain lengths was used in pillaring ZrO2. N-octyl- and decylamine were useful in the construction of the pillar. It is of critical importance to enlarge the interlayer spacing of the HLa by using filling with n-octylamine for the intercalation of the precursor of ZrO2, TiO2, or SiO2. The precursor of ZrO2 or TiO2 could easily be intercalated by exchange with n-octylamine. When pillaring with SiO2 was done, the preparation was not as easy as pillaring with ZrO2 or TiO2. The molar ratio of tetraethoxysilane (TEOS), the concentration of HCl, and the amount of ethanol was closely related in the preparation. The optimum preparation condition was a molar ratio of TEOS:ethanol:HCl (2 or 3 M) of 10:5:0.5 to 1 mol of HLaNb2O7 fully filled with n-octylamine at 40 degrees C. Thus, the materials prepared (by pillaring with ZrO2, TiO2, or SiO2) were used as a catalyst in the dehydration of l-butanol. Enhancement of activity was detected on all the pillared catalysts. It was caused by interaction between the pillaring material and the host matrix. The TiO2 pillared catalyst exhibited the highest activity in hydration, followed by the ZrO2 and SiO2 pillared catalysts. All of the catalysts that were examined consisted of a large amount of mesopore, in which the TiO2 pillared catalyst exhibited the presence of a larger ratio of mesopore, as compared with other catalysts.