Abstract <p>This article presents the results of a study of the composition of oxides formed on surface of the laser impact zone (LIZ) in air of 9KhS, R6М5 and R9K5 tool steels, differing in chemical composition and degree of alloying. Using X-ray photoelectron spectroscopy, it was found that the formed oxide films have a qualitatively matching “layered” structure and differ significantly from each other both in overall thickness and in the thicknesses of the oxide films of different phase composition included in them. It is shown that the formed film is largely multilayered and multicomponent. For alloyed tool steels, a significant redistribution of alloying element concentrations along the LIZ depth was found, which determines the composition of the formed oxides and their location relative to the base material. It is noted that, regardless of the steel composition, the oxide film outer layer on the LIZ surface consists mainly of a mixture of FeO and Fe₂O₃ oxides; deeper towards the base metal, there is a Fe₃O₄ layer and a mixture of higher oxides of alloying elements located in the following sequence deep from the LIZ surface: WO₃, V₂O₅, MoO₂, Cr₂O₃, and CoO. For R9K5 steel, the selective enrichment of the surface in W and Mo atoms was found, leading to strengthening of grain boundaries and the appearance of a local hardened layer at a depth of 90 nm. It was found that the oxide film integral thickness on the LIZ surface of the studied steels does not exceed 200–250 nm.</p>