Electron-diffraction photographs of some natural and synthetic mullites and a typical sillimanite have been obtained and are interpreted using diffraction data due to Agrell and Smith. The position and diffuseness of mullite reflections (h0l) with l = ½ have been re-studied. In such reciprocal lattice sections maxima are symmetrically disposed in pairs about the positions of sillimanite reflections with l odd. They lie on a* rows and show different separations in the specimens studied. These diffraction conditions are closely analogous to those observed in the intermediate plagioclases (paired ‘e’ maxima) and in nepheline, and a similar explanation is envisaged in terms of antiphase domain structure. Intimate association of a mullite-type phase and sillimanite is shown to result from the breakdown of muscovite in a thermal metamorphic aureole, and a chemical analysis of a natural Fe,Ti-bearing mullite from a spinel-mullite buchite in the same aureole, is presented.