The present work is dedicated to investigating the occurrence of the a þ e equilibrium at temperatures typically applied for nitrocarburizing treatments. To this end, pearlitic Fe-C specimens were treated between 823 K and 863 K (550°C and 590°C) in gaseous nitriding and gaseous nitrocarburizing atmospheres, allowing control of the chemical potentials of N and C. Subsequently, the resulting compound-layer microstructures were investigated using light microscopy and X-ray diffraction. Thermodynamic calculations, adopting several models for the Fe-N-C system from the literature, were performed, showing significantly different predictions for both the sequence of the invariant reactions and their temperatures. Comparison of the experimental data and the theoretical calculations led to the conclusion that none of the models from the literature is able to realistically describe the experimentally observed constitution in the Fe-N-C system in the considered temperature range. Values/value ranges for the temperatures of the invariant reactions were obtained.