Abstract: Allophanes with SiO2/Al2O3 molar ratios from 1.38 to 1.92 were heated at temperatures up to 500°C, and the changes induced were investigated by means of infrared spectroscopy (IR) and X-ray powder diffraction (XRD). Heat treatment caused the IR absorption band near 1000 cm−1 due to Si-O stretching to shift towards higher frequencies, and the band near 450 cm−1 due to O-Si-O bending to increase markedly in intensity. These results are probably due to condensation of SiO tetrahedra, following breakdown of Si-O-Al linkages and dehydroxylation of SiOH groups. Concurrent intensity increase of the IR absorption at about 700 cm−1 suggested an increase in the amount of 4-coordinated Al in the heated materials. ‘Imogolite structures’ were decomposed progressively at higher temperatures and were almost absent at about 400°C, as indicated by the weakening and disappearance of the IR band at 348 cm−1 and of the XRD reflections at 2.25 and 1.40 Å. The XRD reflection at 3.3–3.45 Å shifted to about 3.6 Å, probably as a result of thermal condensation of the silica component. The observed thermal changes were much greater for samples with low SiO2Al2O3 ratios (1.38–1.51) than for those with high ratios (1.81–1.92), indicating a lower thermal stability for the former materials. Thus, the thermal stability of allophanes appears to be related to the content of ‘imogolite structures’ and to the polymerization status of the silica component.