In this paper, a method for quantitative determination of spectral distributions of primary radiation from X-ray tubes for diffraction and X-ray fluorescent spectral analysis is presented. The instrument used for this purpose is a diffractometer with a proportional-scintillation counter and a LiF analyzing crystal. The intensity distributions of primary X-ray spectrum obtained using a LiF analyzer are determined. The experimental values of the X-ray intensities of various wavelengths must be expressed in terms of intensities just emitted from the X-ray tube window. For the fluorescent X-ray tubes, several spectral distributions of different directions of primary X-ray beam must be determined and then the mean values of these data are calculated in order to obtain the effective spectral distributions. The errors of the spectral distribution data and its influence on the practical applications such as the fundamental parameter method are discussed.