This paper presents a new method to separate interfering spectra obtained in wavelength dispersive x-ray fluorescence spectrometry (WDXRF). This method permits improved results to be obtained, compared to conventional analytical results and enables the determination of chemical species of the same element without chemical separation. This is done by separation of the spectra due to electronic transitions of the valence electrons. The Rietveld method  overcomes the problem of superimposed peaks of the species present in the specimen and simultaneously enables determination of the species and does not require standard specimens and calibration curves. This signifies a marked improvement in comparison to other techniques. Specimen surface preparation to obtain spectra is a critical stage and its effects can be minimized by using Rietveld refinement, which permits the determination of intensity relationships of superimposed peaks with the aid of mathematical models. This establishes the basic conditions to obtain more accurate results in quantitative analysis. In the determination of chemical species, it is possible to separate, for example, Cr (III) and Cr (IV), with almost 100% superimposition.