AbstractA new empirical mathematical method for inter‐element effect corrections in XRF analysis is presented. It is based on a special theoretical description of XRF phenomena called OMX (operator model of x‐ray fluorescence), presuming a discrete layer model of the sample structure and using mathematical operators to describe the interaction between sample layers and exciting radiation. The operators formed generally as spectral distributions may be simplified into the matrix form for practical application. The effectiveness of the proposed method was verified experimentally by analysing samples of glass and glass raw materi