Abstract: The quantitatively detection of U(Ⅵ) in 30%TBP/kerosene in Purex process was studied. The baseline of the Raman spectra was corrected, and the Raman band of U(Ⅵ) which is considered as symmetric stretching mode ν¹(860 cm^-1) and the band of the organic solvent located at 1065 cm^-1 were selected as quantitative peak and internal standard reference peak, respectively. Take the ratio of the intensities as relative peak intensity, the standard curve was plotted, which is y =0.0636x+0.357 with r²=0.999 in the range of 5.0-107.0 g/L of U(Ⅵ). The standard curve using the internal standard method shows good stability, which changes to y=0.062 4x+0.489 with r²=0.999 after 75 d. The analytical precisions and slopes of the two standard curves show no significant differences when significance level α is equal to 0.05 by F test and t test. The linearity shows good repeatability, thus it can be used for a long period without refreshing it. With the method of internal standard, different containers had little effect on the Raman spectra of uranyl organic solutions, thus the detection can be conducted through the container walls, which had the advantage of simplifying the detection. The detection of U(Ⅵ) in five containers shows the relative deviations of no more than 3.7%, therefore, it has no need to change the containers when detecting the samples. Take the use of the internal standard method, then the integral time and the laser power have little influence on the determination. Thus the parameters can be selected to meet the need of detecting uranyl solutions with different concentrations.