Summary: The thermal disintegration of crocidolite has been investigated with X-ray powder and rotation photographs. Initial disintegration products include monoclinic pyroxene, iron oxide phases, and eristobalite as a pseudomorph of the original fibre bundles but at about 1000° C fusion occurs due to incongruent melting of the pyroxene. The products are strongly oriented along the fibre axis and full orientation relationships have been deduced with the aid of structural models. From these relationships it is suggested that regions of the amphibole structure on (100) are retained in the product phases without change in orientation.