The catalytic activity of a series of mixed oxides obtained by the thermal decomposition of hydrotalcite-like precursors was assessed for the alkoxylation of n-butanol with ethylene oxide. The calcination products of a decavanadate intercalated magnesium-aluminium layered double hydroxide were shown to possess extremely high activity for the alkoxylation reaction achieving up to 100% conversion in batch reaction. In all cases, the catalysts exhibit a much higher selectivity towards the monoglycol adduct than that obtained with the industrial catalyst.