This work compares the performance of X-ray tube induced and synchrotron induced energy dispersive X-ray fluorescence in generating scattering profiles when organic samples are irradiated. In the first case, this effect produces sharper peaks, well defined in the spectra, whereas synchrotron-induced scatter are seen as broad bands. These effects may be used for classifying simple materials like graphite, coke, activated carbon and carbon nanotubes, all having the same composition but different structures, using multivariate data analysis. In a second sample set, the method was applied to liquid samples of different alcohols (methanol, ethanol, 1-propanol and 2-propanol). Classifications were obtained in both cases independent of the X-ray source (synchrotron radiation or X-ray tube radiation), showing that the use of chemometric tools combined with X-ray spectrometry can efficiently distinguish organic samples by using scattering effects.