The selective extraction of Cr(VI) from waste pickling solution of the stainless steel-cold rolled plate process by hydrophobic hollow fiber supported liquid membrane (HFSLM) was investigated. The effects of various parameters--types of organic extractants, i.e., metyl trioctylammonium chloride (Aliquat 336), tri-n-octylamine (TOA), tri-n-butyl phosphate (TBP) and the mixture of Aliquat 336 and TBP, concentration of the selected extractant, types of stripping solutions (NaCl and NaOH), pH and concentration of the selected stripping solution, and the operating temperature--were studied. The feed and stripping solutions flowed countercurrently. The results showed that the coexisting contamination in spent pickling solution of Fe(II) and Ni(II) ions had no significant effect on Cr(VI) extraction. Among the extractants used in this study, Aliquat 336 was a specific carrier to attain the highest percentage of Cr(VI) extraction. About 70% extraction was achieved by using 0.11M Aliquat 336 and 0.5M NaCl at pH 7. The percentage of stripping slightly increased when the concentration of NaCl increased. In addition, it was found that the operating temperature of 20, 30, 40, and 50 ℃ had almost no influence on the percentages of extraction and stripping of Cr(VI). The calculated diffusion energy of Cr(VI) extraction was 15.14 kJ/mol.