Abstract: The substantial arsenic (As) content present in arsenic-containing bio-leaching residue (ABR) presents noteworthy environmental challenges attributable to its inherent instability and susceptibility to leaching. Given its elevated calcium sulfate content, ABR exhibits considerable promise for industrial applications. This study delved into the feasibility of utilizing ABR as a source of sulfates for producing super sulfated cement (SSC), offering an innovative binder for cemented paste backfill (CPB). Thermal treatment at varying temperatures of 150, 350, 600, and 800°C was employed to modify ABR’s performance. The investigation encompassed the examination of phase transformations and alterations in the chemical composition of As within ABR. Subsequently, the hydration characteristics of SSC utilizing ABR, with or without thermal treatment, were studied, encompassing reaction kinetics, setting time, strength development, and microstructure. The findings revealed that thermal treatment changed the calcium sulfate structure in ABR, consequently impacting the resultant sample performance. Notably, calcination at 600°C demonstrated optimal modification effects on both early and long-term strength attributes. This enhanced performance can be attributed to the augmented formation of reaction products and a densified microstructure. Furthermore, the thermal treatment elicited modifications in the chemical As fractions within ABR, with limited impact on the As immobilization capacity of the prepared binders.