It has been generally accepted for long that water molecules are integral parts of layered double hydroxides (LDHs). It is even thought that in the absence of water molecules, there is no LDH structure. It is shown in this contribution that via the solvolysis of Mg-or Ca-alkoxides and Al-alkoxide with methanol or propanol and co-precipitated in methanolic methoxide, waterfree LDH-like structures could be constructed. These novel LDH-like materials proved to be more active and selective catalysts in a Knoevenagel condensation than the corresponding 'classical' LDHs. IMPACT STATEMENT Synthesis, thought to be not possible to prepare, characterization and a catalytic application of water-free LDHs are described. Water molecules are replaced by small alcohol molecules in the interlayer space.