The validity of controlling interfacial toughness in reaction-formed composites was explored using solid-state reaction processing and microanalysis techniques. A variety of rare-earth oxides was added to a yttrium aluminum garnet (YAG)/alumina powder mixture and then melted in air. Some melts retained the crystallography and microstructure of the pure, binary YAG–alumina eutectic. Using scanning transmission electron microscopy in conjunction with energy dispersive X-ray spectroscopy, rare-earth ions were observed both to segregate to the YAG/alumina interface and to form a third phase. Some evidence of increased crack deflection at these interfaces was observed via indentation fracture.