Abstract: A new extractive spectrophotometry for determination of trace chromium(Ⅵ) was established.In KCl-HCl buffer solution of pH=2.0 and at the room temperature,chromium(Ⅵ) could react with diphenylcarbazone(DPCO) to form a stable complex [n(Cr(Ⅵ))∶n(DPCO)=1∶2],and Cr(Ⅵ) in Cr(Ⅵ)-DPCO complex can be extracted by PEG-(NH<SUB>4</SUB>)<SUB>2</SUB>SO<SUB>4</SUB> completely.Results showed that the maximum absorption wavelength of the complex in PEG phase was 548 nm with the apparent molar absorptivity of 3.12×10<SUP>4</SUP> L/(mol·cm);Beer′s law was obeyed in the mass concentration range of 0~2.5 mg/L for Cr(Ⅵ);Most of common ions did not interfere in the determination of chromium(Ⅵ).This proposed method has been applied in the determination of trace chromium(Ⅵ) in chromic nitrate and chromic chloride with satisfactory results.