<p>This study uses artificial stone waste residue (ASWR) as a calcium source to replace calcium carbonate. Through co-calcination with V–Cr-bearing reduction slag (VCRS) followed by alkali leaching, vanadium and chromium can be efficiently separated. Orthogonal experiments were employed to systematically optimize key parameters—including ASWR addition amount, calcination temperature, and calcination time—to evaluate their effects on the leaching behaviors of vanadium and chromium. The separation mechanism is as follows: during calcination, CaO released from ASWR preferentially combines with vanadium to form alkali-soluble calcium vanadate, while chromium is stabilized as insoluble chromium oxides (Cr₂O₃) within the slag. Subsequent alkaline leaching selectively extracts vanadium into solution by exploiting the conversion of calcium vanadate into less soluble calcium carbonate upon reaction with sodium carbonate, thereby enriching chromium in the solid residue. Single-factor experiments further examined the influence of Na₂CO₃ concentration, leaching temperature, time, and liquid-to-solid ratio on leaching efficiency. Under optimal conditions (30% ASWR addition, calcination at 950&#xa0;°C for 3&#xa0;h, 150&#xa0;g/L Na₂CO₃, leaching at 90&#xa0;°C for 180&#xa0;min, L/S ratio of 8:1), a vanadium leaching rate of 95.18% was achieved compared with only 1.16% for chromium, demonstrating the exceptional selectivity of the process. This work presents a novel strategy and theoretical foundation for the synergistic, high-value utilization of these two types of industrial waste.</p> Graphical Abstract <p></p>