In many applications, the radionuclidic purity of a radioactive substance is a crucial property. It involves, for example, the production of radiopharmaceuticals or reference standards used in metrology. However, the identification of admixtures is not straightforward for certain nuclides. The paper presents a technique for the determination of radionuclide impurities in the mixtures of pure beta-emitting nuclides. The proposed method is based on the comparison of measured beta spectra with the detector responses to individual radionuclides. These are obtained using a Monte Carlo calculation performed in the geometry corresponding to the accurate description of a measuring assembly.