Alumina is one of the most studied and used ceramic materials, but increasing its fracture toughness is still a challenge for many specific impact applications. Adding a second phase with a low coefficient of thermal expansion (CTE) to an alumina matrix can enhance the matrix’s mechanical properties, reduce its sintering temperature, and increase its toughness by generating compressive stresses on the alumina particle surface. In this study, nanostructured alumina/eucryptite composites were prepared to achieve enhanced toughness. First, eucryptite (Li₂O·Al₂O₃·2SiO₂) nanoparticles were successfully synthesised via colloidal heterocoagulation. These nanoparticles were then used to reinforce alumina matrices through slip casting followed by conventional sintering. Complete crystallisation of eucryptite was achieved at 850 °C with a CTE of 0.46 × 10 ⁻⁶ °C ⁻¹. Transmission electron microscopy analysis revealed that the average particle size was 28.5 ± 14.5 nm. To achieve a relative density of 95.3%, the composite containing 5 vol.% eucryptite required sintering for 1 h at 1400 °C whereas pure alumina required 2 h at 1600 °C. This reduction in sintering temperature (by up to 200 °C) helped to improve the fracture toughness, with the alumina grain size decreasing from 2.3 to 0.9 µm. The advantages of the new composite are the more economically viable and environmentally friendly way of producing the lithium aluminosilicate nanoparticles, compared to the production of ceramic frits at high temperatures (~1500 °C).