The thermochemical treatments of tool steels improve the performance of the components with respect to surface hardness, wear and tribological performance as well as corrosion resistance. Compared to the conventional gas ferritic nitrocarburizing process, the original vacuum oxy-nitrocarburizing is a time-, cost-effective and environmentally-friendly gas process. Because of the oxidizing nature of the gas atmosphere, there is no need to perform subsequent post-oxidation.In this study, a vacuum oxynitrocarburizing process was carried out onto four tool steels (AISI H10, H11, H21 and D2) at 570 degrees C, after hardening and single tempering. The structural analysis of the compound and diffusion layers was performed by optical and electron microscopy, X-ray diffraction and glow discharge optical emission spectrometry (GDOES) methods. A largely monophase epsilon-layer is formed with a carbon accumulation at the substrate adjacent area. The overlaying oxides adjacent to the epsilon-carbonitride phase contained Fe3O4 (magnetite) as a main constituent. A thermodynamic modelling approach was also performed to understand and optimize the process. The "Equilib module" of FactSage software which uses Gibbs energy minimization method, was used to estimate the possible products during vacuum oxynitrocarburising process.