<p>Recovering cadmium from high arsenic-bearing dust while simultaneously immobilizing arsenic offers an effective route for utilizing valuable metals. This study proposes a process involving oxidative acidic leaching, synergistic extraction, and scorodite synthesis to enable cadmium recovery and the environmentally friendly treatment of arsenic. This study is divided into three parts: (i) oxidative acidic leaching of cadmium and arsenic from high arsenic-bearing dust at pH 1.0, with a H₂O₂ dosage of 0.5 and a liquid-to-solid ratio of 20 for 3&#xa0;h, achieving leaching ratios of 98.73% for As and 88.97% for Cd, while 99.52% of lead was converted to PbSO₄ enriched in the residue; (ii) the use of a composite extractant comprising (di(2-ethylhexyl) phosphate) (P204) and versatic10 (V10) at concentrations of 0.2&#xa0;mol/L each to recover Cd²⁺ from the leachate containing CdA₂(HA)_2.6(HB)_0.4 at 25&#xa0;°C and pH_eq = 2.95; and (iii) the immobilization of arsenic in the extracted solution as scorodite under specific conditions (initial pH = 2.0, Fe/As molar ratio = 1.5, temperature = 95&#xa0;°C, and reaction duration = 8&#xa0;h). This process resulted in the precipitation of 99.5% of arsenic as scorodite, with low leachability (0.10&#xa0;mg/L), indicating its suitability for safe storage. Moreover, only 0.04&#xa0;mg/L of arsenic leached from the synthesized scorodite during the synthetic precipitation leaching procedure, demonstrating its stability for safe metallurgical disposal. Overall, this method successfully separates Cd and Pb while immobilizing As from high arsenic-bearing dust, offering a guidance for efficient cadmium resource recovery and environmentally friendly management of As- and Cd-bearing wastes.</p> Graphical Abstract <p></p> <p>XRD pattern (a), FT-IR spectra (b), and SEM images (c) of scorodite synthesized from residual leachate.</p>