The phase composition and the microstructure of multilayer ceramics synthesized by directed laser treatment of ternary powder mixtures of Al2O3–TiO2–Y2O3 have been studied. It is established that at R = 2.34 (where R is TiO2/Y2O3 in mol %) the main phases observed are Y2Ti2O7, α-Al2O3 and a little amount of β-Al2TiO5. The content of the formed phases is determined by the composition of the initial mixtures. The texture of the surface and the microstructure of the formed ceramics depend on the α-Al2O3 and Y2Ti2O7 content. Increasing the content of alumina in the initial mixtures, the surface of the ceramics is saturated by α-Al2O3 crystallites. When a multi-layer synthesis is realized, the Y2Ti2O7 phase is concentrated at the boundary between the two adjacent layers (top and bottom). In the underlying layer, the growth of the corundum crystallites is prolonged due to the additional heating.