Al2O3-Al2TiO5-TiO2 composites can be obtained by the infiltration of molecular titanium precursors into presintered α-Al2O3 (corundum) cylinders. Two titanium tetraalkoxides, and two dialkoxy titanium bis(acetylacetonates) serve as precursors for TiO2 (rutile) and Al2TiO5 (tialite). The precursors were infiltrated as ethanolic solutions. After sintering at 1550, 1600, and 1650°C, the prepared ceramics’ properties were investigated by SEM, in-situ HT-XRD, and conventional XRD. Titanium tetraisopropoxide leads to the highest content of Al2TiO5 in the composite. The more reactive the precursor, considering the Al2O3/precursor interface, the lower and more anisotropic the grain growth, the more homogeneous is the TiO2 contribution and the higher is the content of Al2TiO5. Raising the sintering temperature causes an increase of the crystalline Al2TiO5 con­tent as well as of the grain growth. Moreover, the reactivity of the precursor molecule influences the Ti/(Al + Ti) ratio in the obtained tialite phase.