Double alkoxides of the general formula Mg[Al(OR)4]2 where R is iso-Pr or sec-Bu were prepared by reacting aluminium and magnesium metals together with the alcohol ROH and purified by vacuum distillation. They were characterised by IR, proton and 27Al NMR spectroscopy and MW determination. A magnesium aluminium double alkoxide was also prepared by treating the commercially available aluminium alkoxide ‘Aliso B’ [a mixed aluminium (iso-propoxide)(sec-butoxide)] with magnesium and iso-propanol. Treatment of magnesium aluminium double alkoxides with water and an alkanolamine (preferably triethanolamine) gives a rigid coherent gel. Viscosity measurements and 27Al NMR spectroscopy suggest that the double alkoxide does not break down to its constituents during hydrolysis. The air-dried gel was shown by XRD to convert quantitatively to spinel on firing to 1500°C. The resistance of the double alkoxide moiety to hydrolysis explains the ease of conversion to spinel on firing. The gel has been used to bind alumina and magnesia grain. Gels suitable for binding refractory grain were obtained only when the alkanolamine content corresponded to one alkanolamine group per metal atom. Electron micrographic and XRD studies showed that in fired refractory pieces, the bonding phase was spinel.