The interfacial reaction between Al2O3 (alumina) and a β-Ti alloy has been characterized by transmission electron microscopy, scanning electron microscopy, and X-ray energy-dispersive spectroscopy. Diffusion bonding single-crystal alumina and a β-Ti alloy was found to produce three interfacial regions: a region of intermetallics (Tl3Al and TiAl) located near the alumina interface, an α-Ti region, and a β-Ti region (rich in Mo, the β-phase stabilizer). Of the intermetallics to form, Ti3Al was found to form first and have an aligned, planar interface with the alumina. TiAl formed second and was found to separate grains of Ti3Al and the alumina. Reaction products observed in the diffusion-bonded alumina/β-Ti couples are compared with those observed in metal-matrix composites (MMCs), where a β-Ti alloy matrix is reinforced with alumina fibers. Different coatings used in MMCs are investigated for their ability to prevent the reaction between the matrix and fibers.