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The effective recovery and utilization of elemental sulfur in the direct leach residue (DLR) from zinc oxygen pressure leaching poses a significant challenge. This study analyzes the distribution characteristics of sulfur in DLR and determines its solubility in n -decane at various temperatures. Results indicate a gradual increase in sulfur solubility with temperature, reaching a maximum of 6.84 g/100 mL at 150 °C Utilizing the Apelblat model, a fitting equation of ln X = 88.3–7155.9/ T − 12.0ln T is derived. Under conditions of 130 °C, a liquid–solid ratio of 8:1, a reaction time of 3 min, and a stirring speed of 300 rpm, 99.2% of sulfur in the residue can be dissolved in n -decane. Additionally, this separation process naturally enriches other valuable elements in the residue. The cooling rate significantly influences sulfur purity, with elemental sulfur forming high-quality crystals exhibiting a positive octahedral rhombic morphology at a cooling rate of 0.018 °C/s. Finally, the dissolution mechanism of sulfur in n -decane involves sulfur complexation, and the reliability of the sulfur solubility model is verified. • Achieving good separation of sulfur in direct leaching residue from zinc oxygen pressure leaching. • Realize the harmless and resourceful treatment of direct leaching residue. • Crystallization by slow cooling gives better crystalline ortho-octahedral sulfur. • Analysis of sulfur dissolution mechanism in direct leaching residue. [ABSTRACT FROM AUTHOR]