The article examines the effect of different types of two-layer nanostructured coatings (cVIc and nACVIc) deposited on three types of steel substrates, 45S20, C45E, and 42CrMo4, to determine the resistance to adhesive wear of the substrate/coating system. The samples underwent different heat treatments, including normalising, quenching, and quenching and tempering, followed by PVD (physical vapour deposition) treatment at temperatures of 450 °C (cVIc) and 460 °C (nACVIc). The thickness of the cVIc layers for all three steels ranged from 0.9 to 3.4 μm, while the thickness of the nACVIc layers on all steels was slightly greater, ranging from 1.9 to 3.1 μm. Tribological tests were conducted using the pin-on-disc method, and the results were statistically analysed. Results indicate that steel grade, heat treatment, and PVD coating significantly affect adhesive wear resistance, with the type of PVD coating showing the strongest influence. For all three steels, quenched and uncoated samples exhibited the lowest adhesion wear index values. Normalised and quenched with or without tempering steels coated with cVIc layer exhibit higher resistance to adhesive wear due to better adhesion of the layer compared to the nACVIc coating.