Chemical stabilization is frequently used to stabilize lead (Pb) or arsenate (As), but faces challenges in Pb-As co-contaminated soils because of the antagonistic reactions between chemical stabilizers and contaminants. In this work, we innovated an effective and cost-efficient stepwise steam flash heating (SSFH) strategy to simultaneously immobilize Pb and As, and unraveled the underlying mechanisms. The combination of 1.5% Ca(H2PO4)2 and 2% Fe2(SO4)3 only decreased 1.99% Pb by toxicity characteristic leaching procedure (TCLP-Pb) but increased 17.8% of TCLP-As due to the antagonistic effects. SSFH with Ca(H2PO4)2 in the first step and Fe2(SO4)3 in the second step achieved the minimal TCLP-Pb and TCLP-As of 0.778 and 0.327 mg/L, respectively. It also reduced 69.8% of leachable As in 100-year acid rain simulation, indicating a favorable long-term stabilization performance. Additionally, SSFH approach reduced 43.2% stabilizer dosage and 14.9% cost. X-ray absorption near edge structure (XANES) documented that the stepwise SFH promoted the transformation of Pb(NO3)2 and NaAsO2/NaAsO3/As2O3/As2O5 into stable Pb3(PO4)2 and FeAsO4, preventing the formation of AsO43- and FePO4. Our findings proved the state-of-the-art SSFH approach and unraveled its mechanisms to stabilize Pb and As co-contamination in soils, offering a green and sustainable remediation alternative for the management of heavy metal contaminated sites. A novel stepwise SFH approach can be applied to overcome the stabilizer antagonist effects by separately immobilizing Pb and As in two sequential steps. It also decreased 43.2% of stabilizer dosage and 14.9% of cost comparing to conventional chemical stabilization. This approach can be used for other metal co-contaminated soils facing similar antagonistic challenges, and our work raises a state-of-the-art solution for cost-effective, green and sustainable remediation practices. Display omitted •Innovative stepwise steam flash heating (SSFH) for effective Pb and As immobilization.•SSFH efficiently eliminated the antagonistic effect by stabilizers.•Higher cost-efficiency and favorable long-term immobilization performance in SSFH.•SSFH changes Pb and As immobility mechanism evidenced by XANES.