In thermodynamic modeling of the desulfurization of steel by CaO–SiO2–MgO–Al2O3–B2O3 slag on the basis of HSC 6.12 Chemistry software (Outokumpu), the influence of the temperature (1500–1700°C), the slag basicity (2–5), and the B2O3 content (1–4%)1 on the desulfurization is analyzed. It is found that the sulfur content is reduced with increase in the temperature from 1500 to 1700°C, within the given range of slag basicity. At 1600°C, the sulfur content in the metal is 0.0052% for slag of basicity 2; at 1650°C, by contrast, its content is 0.0048%. Increase in slag basicity from 2 to 5 improves the desulfurization, which increases from 80.7 to 98.7% at 1600°C. If the B2O3 content in the slag rises, desulfurization is impaired. At 1600°C, the sulfur content in the metal may be reduced to 0.0052 and 0.0098% when using slag of basicity 2 with 1 and 4% B2O3, respectively; in the same conditions but with slag of basicity 5, the corresponding values are 0.00036 and 0.00088%, respectively. Note that desulfurization is better for slag without B2O3. According to thermodynamic modeling, metal with 0.0039 and 0.00019% S is obtained at 1600°C when using slag of basicity 2 and 5, respectively, that contains no B2O3. The results obtained by thermodynamic modeling for the desulfurization of metal by CaO–SiO2–MgO–Al2O3–B2O3 slag of basicity 2–5 in the range 1500–1700°C are consistent with experimental data and may be used in improving the desulfurization of steel by slag that contains boron.