Ten kinds of typical materials including sulfides, calcium-based and iron-aluminum-based materials (Fe⁰, ferric salt, Fe₂O₃/Al₂O₃) were used to stabilize arsenic-containing slag. Five single chemical extraction methods simulating different exposure conditions were used to screen out materials with better stabilization effect. The mechanism underlying arsenic stabilization by typical materials was revealed by the analysis of continuous chemical extraction and microstructure characterization. The results demonstrated that Na₂S·9H₂O showed the best stabilization effect under natural condition. While, Fe⁰ exhibited the strongest arsenic stabilization ability followed by FeSO₄·7H₂O under other conditions. Fe⁰ is suitable for arsenic stabilization under organic weak acid and strong acid rain conditions. FeSO₄·7H₂O was effective under all conditions, however its effect varied greatly. It showed the best effect for arsenic stabilization under weak organic acid condition, and TCLP-As leaching was reduced to 1.50μg/L with arsenic stabilization rate of 99.98%. FeSO₄·7H₂O mainly reduced the extractable weak acid state, and converted the non-specific/specific adsorption state, amorphous and weak crystalline iron-aluminium or iron-manganese state into crystalline iron-aluminium or iron-manganese state and residue state. A small amount of insoluble iron and arsenic minerals (FeAsO₄·2H₂O and FeAsS) were formed after treatment.