KR (Kanbara Reaction) desulfurization slag is a solid waste that is not sufficiently utilized. This is because the KR desulfurization slag contains 1–2.5% sulfur, which is directly used in steel smelting to increase the sulfur content in molten steel. Therefore, the possibility of oxidation desulfurization of KR desulfurization slag was studied in this study. Experiments were conducted to investigate the possibility of removing sulfur from used KR (Kambara Reaction) slag with oxidation. The KR slag samples were treated with oxidative desulfurization in the oxygen partial pressure range of 0.05 bar–1.00 bar, with a gas flow rate ranging from 2 L min−1 to 6 L min−1, and at a temperature of 1420 °C. X-ray diffraction (XRD), an infrared carbon sulfur analyzer, and scanning electron microscopy–energy dispersive X-ray spectrometry (SEM–EDS) analysis were used to reveal the oxidative desulfurization mechanism of KR desulfurization slag. At low oxygen pressure (PO2 < 0.20 bar), the desulfurization rate of slag oxidized for 120 min increased with the increase in oxygen partial pressure. At high oxygen pressure (PO2 ≥ 0.20 bar), the desulfurization rate of slag samples did not change with the change in oxygen partial pressure, and the desulfurization rate was higher than 93.5%. At low oxygen pressure (PO2 < 0.20 bar), the residual sulfur in the slag after oxidation still existed in the slag as the CaS phase. At high oxygen pressure (PO2 ≥ 0.20 bar), the residual sulfur in the slag oxidized from the CaS phase to the 11CaO·7Al2O3·CaS phase in the slag. The sulfur removal rate was directly correlated with the slag surface area and the flow rate of the reaction gas, and it increased with an increase in both surface area and gas flow rate.