<p>With the progressive depletion of high-grade copper resources, arsenic-bearing copper ores have become increasingly important feedstocks for copper smelting. In this study, a precisely controlled vertical tube furnace system was employed to investigate the arsenic volatilization behavior and phase evolution of a high-arsenic copper concentrate under varying temperatures (600–1200°C), residence times (0–30&#xa0;s), and oxygen atmospheres (air, 5 vol%O₂, and Ar). Elemental enrichment degree analysis reveals that increasing reaction temperature and residence time significantly promote arsenic volatilization. At 600°C, arsenic volatilization remains limited, whereas, at 1200°C, the arsenic is almost completely transferred to the gas phase. With increasing temperature, the influence of oxygen partial pressure becomes significantly weakened. Kinetic analysis conducted in the temperature range of 900–1200°C indicates that the reaction order with respect to oxygen partial pressure is lower than 0.1, suggesting a weak dependence on oxygen potential at elevated temperatures. Using a unified regression approach, a high-temperature kinetic rate equation for arsenic volatilization was established. This study provides critical experimental data and mechanistic insights for understanding arsenic migration and removal mechanisms in the suspension zone of copper flash smelting. Moreover, it provides guidance for on-site process parameter adjustment, facilitating the directional enrichment of arsenic for effective removal or valorization.</p>