The effect of Ti addition on as-cast austenite (γ) structure of S45C steel has been investigated. The as-cast γ structure without the Ti addition consists of coarse columnar grains. The Ti addition leads to formation of equiaxed γ-grains and also grain refinement of the γ structure. Fully equiaxed and very fine γ-grain structure forms in a limited range of Ti addition of 0.13 to 0.17 wt%. The thermodynamic calculation of phase diagram showed that Ti carbonitride crystallizes as a primary phase in this composition range. The formation of the very fine equiaxed γ-grain structure originates from the columnar-to-equiaxed transition (CET) in δ-dendrite solidification induced by the primary Ti carbonitride particles. These particles act as the nucleation sites of the equiaxed δ-dendrite. The experimental results are suggestive of existence of finer Ti carbonitride particles retarding the grain growth of γ-phase after the peritectic transformation, which leads to the refinement of the as-cast γ structure.