The aim of this study was to investigate the correlation between the basic and catalytic properties of brucite and Mg,Al-layered double hydroxides (Mg,Al-LDHs) in the reaction of propylene oxide with methanol. The basic properties of the solids were investigated by FT-IR spectroscopy using CDCl3 as probe molecule and Hammett acidity titration with n-butylamine and benzoic acid. Both the increase in the activation temperature and the decrease in Al content favored the increase in the basicity of Mg,Al-LDH. The nature of "Mn+-O2- Lewis acid-base" pairs was a key factor to control the catalytic behavior of the solids. The length of the M-O bond, the basicity of the oxygen ion and the strength of the metal ion on the surface affected the catalytic activity of the solids and their isomer selectivity in the reaction between methanol and propylene oxide to form 1-methoxy-2-propanol. It was demonstrated that brucite(150) can be applied as catalyst for at least four successive cycles without loss of activity. (C) 2016 Elsevier B.V. All rights reserved.