The mineralogical and chemical characteristics of As solid phases in arsenic-rich mine tailings from the Nakdong As–Bi mine in Korea was investigated. The tailings generated from the ore roasting process contained 4.36% of As whereas the concentration was up to 20.2% in some tailings from the cyanidation process for the Au extraction. Thin indurated layers and other secondary precipitates had formed at the surfaces of the tailings piles and the As contents of the hardened layers varied from 2.87 to 16.0%. Scorodite and iron arsenate (Fe₃AsO₇) were the primary As-bearing crystalline minerals. Others such as arsenolamprite, bernardite and titanium oxide arsenate were also found. The amorphous As–Fe phases often showed framboidal aggregates and gel type textures with desiccation cracks. Sequential extraction results also showed that 55.7–91.1% of the As in tailings were NH₄-oxalate extractable As, further confirmed the predominance of amorphous As–Fe solid phases. When the tailings were equilibrated with de-ionized water, the solution exhibited extremely acidic conditions (pH 2.01–3.10) and high concentrations of dissolved As (up to 29.5 mg L⁻¹), indicating high potentials for As to be released during rainfall events. The downstream water was affected by drainage from tailings and contained 12.7–522 μg L⁻¹ of As. The amorphous As–Fe phases in tailings have not entirely been stabilized through the long term natural weathering processes. To remediate the environmental harms they had caused, anthropogenic interventions to stabilize or immobilize As in the tailings pile should be explored.