The paper presents the study results of CrN/TiN multi-layer coatings, as well as single-layer TiN and CrN coatings on Cr12MoV cold work die steel deposited by the vacuum-arc plasma-assisted method. Three CrN/TiN coatings of 8-, 16-, and 32-layers were deposited, in which the thickness of each layer was 500 nm, 250 nm and 125 nm, respectively. All of the coatings reveal a face-centered cubic structure with highly oriented (111) growth. The hardness of the CrN/TiN multi-layer coatings was about 27 GPa. Changing the architecture of CrN/TiN multi-layer coatings by reducing the thickness of the CrN and TiN layers from 500 nm to 125 nm promotes a smooth decrease in both the wear parameter and the coefficient of friction. By using an X-ray phase analysis with synchrotron radiation, it was found that 32-layer CrN/TiN coating retained thermal stability during heating in air to a temperature of 1120–1125 °C, and in a vacuum at least to a temperature of 1200 °C.