High-strength tire cord steel is mainly used in radial ply tires, but the presence of brittle Ti inclusions can cause failure of the wires and jeopardize their performance in production. In order to control the titanium content during steel production, a thermodynamic model for predicting the titanium distribution ratio between CaO−SiO2−Al2O3−MgO−FeO−MnO−TiO2 slags during the ladle furnace (LF) refining process at 1853 K has been established based on the ion−molecule coexistence theory (IMCT), combined with industrial measurements, and the effect of basicity on the titanium distribution ratio was discussed. The results showed that the titanium distribution ratio predicted by the developed IMCT exhibited a dependable agreement with the measurements, and the optical basicity is suggested to reflect the correlation between basicity and the titanium distribution ratio. Furthermore, quantitative titanium distribution ratios of TiO2, CaO·TiO2, MgO·TiO2, FeO·TiO2, and MnO·TiO2 were acquired by the IMCT model, respectively. Calculation results revealed that the structural unit CaO plays a pivotal role in the slags in the de-titanium process.