Series of Al-, Ga-, and Zr,Al-pillared clays (Al-MM, Ga-MM, and Zr,Al-MM) were prepared through the intercalation of Al-, Ga-, and Zr-polyoxocations into three layered aluminosilicates with various textural properties and chemical compositions. Zr,Al-phases with the structure of bayerite-boehmite were also synthesized using Al and Zr oligomeric solutions, prepared from aluminum chloride and zirconium oxychloride, respectively, as metal sources, with Zr/Al ratios of 0-0.143. All materials were characterized by X-ray diffraction; elemental analysis; DR-UV-vis, FTIR, and Al-27 MAS NMR spectroscopies; and N-2 adsorption/desorption analysis. FTIR spectroscopy using pyridine, benzonitrile, and deuterated chloroform as probe molecules was used to investigate the acid-base properties of the solids. The catalytic performance of these materials was investigated in the synthesis of 1-methoxy-2-propanol from methanol and propylene oxide. It was found that the catalytic properties of Zr,Al-pillared clays depended on the textural properties (pore diameter), chemical composition (Si/Al molar ratio and Zr content), and type of Al salt (nitrate or chloride) used as the Al source for the preparation of the pillaring solution. The type of metal cation in the polyoxocations affected the reaction rate and isomer selectivity. Al-MM was found to exhibit a higher catalytic efficiency than Ga-MM and Zr-MM.