Abstract <p>A method for determining the carbon content of carbonate–aluminosilicate glasses by electron probe microanalysis is proposed and implemented. To take into account the C<i>K</i>_α signal arising due to the conductive carbon coating and beam-induced carbon contamination, we used a calibration approach with carbonate reference samples of different carbon concentrations. The analytical signal was determined as the area under the first C<i>K</i>_α peak in the recorded X-ray spectrum, which ensured the account of the effects of carbon–oxygen bonding and interactions with other elements on the C<i>K</i>_α peak shape and position. Optimal conditions for recording spectra in the C<i>K</i>_α region were found for accurate carbon determination. Linear calibration curves obtained at 5 kV using carbonate standards were highly reproducible, with relative standard deviations of 1–3%. The method ensures limits of detection of 0.2–0.4 wt % and limits of quantification of 0.6–1.2 wt %.</p>