The influences of additives on the phase transformation, occurrence state, and the interface of the Ti component in Ti-bearing blast furnace slag were investigated. After oxidation, most of the Ti component in the slag was enriched into the perovskite phase, which served as the Ti-rich phase during the crystallization process. The phase transformation, occurrence state, and the interface of the Ti component were observed to be affected by the addition of different types of agents. During the oxidation process, titanaugite and Ti-rich diopside phases gradually transformed into non-Ti phases (anorthite: CaMgSi₂O₆ and CaAl₂Si₂O₈) in the form of dendrites or columns, which were observed to be distributed at the surface of the perovskite phase. Several more cracks appeared along the grain boundaries of the perovskite phase after the addition of P₂O₅, facilitating the liberation of the perovskite phase. Composite additives combining both an acid and a base, such as CaO + CaF₂ or P₂O₅ + CaF₂, were used. We observed that the disadvantages of using single additives were successfully overcome.