Sulfate roasting is a critical pyrometallurgical pre-treatment for extracting Cu and Co from low-grade Cu–Co–Fe sulfide ores, yet conventional phase diagrams provide limited quantitative guidance for process control. To address this gap, a multicomponent/multiphase thermodynamic equilibrium model based on Gibbs free energy minimization was developed to systematically investigate the oxidative roasting behavior of single sulfides (Cu₂S, CoS₂, FeS₂) and their ternary mixture, with respect to air supply, temperature, and total pressure. The model reveals that each sulfide follows distinct, temperature-dependent phase transformation pathways: Cu₂S forms the acid-leachable product CuO·CuSO₄ at temperatures ≤ 588 °C with a stoichiometric air supply of 11.9 mol, transitioning to oxides at ≥800 °C; CoS₂ converts completely to CoSO₄ below 727 °C and to CoO at higher temperatures; FeS₂ yields sulfate phases at low temperatures and iron oxides above 654 °C. In the ternary Cu₂S–CoS₂–FeS₂ system, competitive oxidation reactions produce refractory mixed oxides (CuO·Fe₂O₃, CoO·Fe₂O₃) whose formation is governed by temperature, air supply, and sulfide molar ratios. The results demonstrate that low-temperature roasting (≤641 °C) with precisely controlled air supply maximizes the formation of water-soluble sulfates, providing a quantitative thermodynamic basis for process optimization and enhanced recovery of Cu and Co from complex sulfide ores.