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In this study, the anatase–rutile phase fraction of TiO₂, which would play a vital role in the solid-state synthesis of BaTiO₃, was controlled to form a composite phase. The composite TiO₂ was applied to a solid-state synthesis reaction, and the tetragonality, dielectric properties, and microstructure of the resulting BaTiO₃ powders were analyzed under different synthesis conditions of TiO₂. Furthermore, a comparative analysis of solid-state-synthesized BaTiO₃ powders prepared using anatase, rutile, and mixed (anatase + rutile) TiO₂ was performed to elucidate the mechanism of improvement in the sintering behavior and dielectric properties of the BaTiO₃ powder synthesized using the composite TiO₂. As a result of applying composite TiO₂, BaTiO₃ powder with excellent tetragonality was synthesized. In addition, it is effective in powder growth and the control of powder morphology, so sintering and dielectric properties can be improved at relatively low temperatures.