Analysis of high‐resolution EDS particle X‐ray emission spectra is typically more complex than standard Si(Li) detector spectra analysis because of the need to carefully account for contributions from minor and satellite transitions. In this work, a pure Yb2O3 sample was irradiated at the high‐resolution high‐energy‐particle X‐ray emission setup of C2TN, and simultaneous CdTe and X‐ray microcalorimeter spectrometer spectra were collected covering both L and K lines. The Yb2O3 high‐resolution spectrum was analysed using the DT2 code that allows to include in the fitting model both diagram lines as well as multi‐ionisation satellites, radiative auger emission, energy shifted lines (chemical effects) and any other contributions. In this communication, we present the results of the fit of the high‐resolution Yb2O3 spectrum and discuss details and problems related to the transitions energy, intensity and line width data. Copyright © 2017 John Wiley & Sons, Ltd.