Abstract: The hexavalent chromium Cr(Ⅵ) content in chromium slag field soils typically ranges from tens to thousands of mg/kg, far exceeding the background values of ordinary soils and exhibiting complex matrices. Existing methods for determining high-content Cr(Ⅵ) in such contaminated sites are susceptible to matrix interferences. This study introduces a synergistic extraction method based on the industrial standard HJ 1082—2019 alkaline extraction solution, enhanced by the addition of EDTA chelating agent and Triton X-100 surfactant. This method improves extraction efficiency and suppresses Cr(Ⅲ) oxidation through dual mechanisms of chemical chelation and physical dispersion. Optimal extraction conditions, determined via orthogonal experiments, include∶12mL alkaline extraction solution, 90°C extraction temperature, 80 min extraction time, 3mL Triton X-100, 12mL EDTA, and a solid-to-liquid ratio of 1∶54 (g∶mL). Under the optimal extraction conditions, the recovery rate of Cr(Ⅵ) in soil reached 96.8%, and the number of extractions was reduced from 6 times in the HJ 1082—2019 standard method to 2 times in this method. Cr(Ⅵ) quantification was performed using inductively coupled plasma optical emission spectrometry (ICP-OES), with high-salt matrix interferences mitigated by adding 2.0g of 001×7 strong acid cation exchange resin. The method exhibited excellent linearity (0-8.00mg/L), a detection limit of 0.30mg/kg, a quantification limit of 1.01mg/kg, and an upper detection limit of 3200mg/kg. Validation using certified reference materials (GBW(E)070255, RMH-A043) and two high-content Cr(Ⅵ) self-prepared samples demonstrated close agreement between measured and certified values (relative errors from −2.87% to −0.69%) and low relative standard deviations (RSD＜5.00%). Compared to flame atomic absorption spectrometry, this method offers superior matrix interference resistance and broader applicability, and has been successfully applied to Cr(Ⅵ) determination in soils from a chromium slag field in North China.