AbstractThe overlapping of characteristic spectral lines of two or more elemental constituents of a sample has always been a drawback in x‐ray fluorescence analysis. A new approach to solve this problem is presented, based in the excitation at two different energies. The results show that it is possible to calculate the concentration of elements with overlapped lines with high accuracy. We thus avoid the use of other means to obtain the needed number of spectral lines, such as secondary characteristic lines, which usually have a low peak to background ratio, or to recur to the line fraction (i.e. Kβ/Kα), which is matrix depend