Uni-modal and bi-modal microstructures were concurrently observed in a TiO 2-doped -Al 2O 3 ceramic material with some SiO 2 impurity. The segregation of Ti and Si to grain boundaries was systematically evaluated to reveal their role at the start of anisotropic grain growth. In general, in the bi-modal area grain boundaries exhibit higher Si excess than those in the uni-modal area. However, the basal plane of anisotropic grains was always found to contain more segregated Si while the non-basal planes were found to contain less Si. Such enrichment of SiO 2 was also found at the basal planes of equiaxed grains in the uni-modal area, which occurred in the initial stage of anisotropic grain growth. Before and after this stage, the grain boundary composition was relatively uniform with the mole ratio of SiO 2 to TiO 2 as 2.3: 1 and 5.8: 1, respectively. The latter should be related to the composition of eutectic liquid formed during the sintering, which is responsible for the development of the bi-modal microstructure.