This study involved the investigation of the effects of the continuous cooling process conditions on the crystallization and liberation characteristics of anosovite in Ti-bearing titanomagnetite smelting slag. The samples were heated until melting and then the temperature was held at 1650℃ for nearly 0.5 h; subsequently, the samples were cooled at different cooling rates to different temperatures and water-quenched after being held for different times at these temperatures. Last, the obtained crystallized samples were used to analyze the crystallization and liberation characteristics. It was found that, during the continuous cooling process, anosovite particles were found to initially precipitate in the slag at a relatively high crystallization temperature, showing the characteristics of euhedral crystal. The precipitation and growth of anosovite grain is strong and the morphology of anosovite was basically not affected by the continuous cooling conditions. From the morphology perspective, the formed anosovite is an excellent Ti-rich phase to be selective separated. The formation of spinel and diopside is negative for the liberation and selective separation of the anosovite phase. The crystallization diagrams of TiO₂-MgO-CaO-SiO₂-Al₂O₃-FeO slag undergoing different continuous cooling processes were constructed to help to determine the optimal continuous cooling-quenching condition for selective separation of anosovite. Moreover, the addition of B₂O₃ can enlarge the range of the optimal continuous cooling-quenching conditions for selective separation of anosovite.