The paper concerns the process of the composite: ‘nitrided layer-PAPVD coating’ creation on substrates made of hot working steel. The composite properties are determined by the appropriate selection of coating parameters and nitrided case structure. The results of research concerning the influence of a method of substrate nitriding and the created nitrided case structure on the adhesion and plastic properties of the PAPVD coatings are presented in the paper. Substrates made of hot working steel EN X35CrMoV5 (0.4% C, 0.4% Mn, 1.0% Si, 5.0% Cr, 1.3% Mo, 0.3% V) underwent different processes of thermo-chemical and finishing surface treatment in order to obtain a nitrided layer of a different structure: Feα(N), Feα(N)+‘white layer’-Ë,γ′. Research was carried out for nitrided layers created in a controlled gas nitriding process. Four different coatings of nitrides, TiN, Ti(C,N), CrN, (Ti,Cr)N, were deposited on substrates with nitrided layers using the arc-vacuum method and the MZ-383 equipment manufactured by Metaplas Ionon. For composite nitrided layer/PAPVD coating’ prepared in this way, the authors carried out a metallographic analysis, using the optical microscope Neophot32, and measurements of surface roughness of the deposited nitrides. The X-ray phase analysis carried out on the Philips PW1830 diffractometer enabled the phase composition of nitrided layers and the phase composition and the lattice parameter of the deposited PAPVD coatings to be determined. Then, the authors carried out measurements of the coating adhesion for all investigated composites using the scratch-test method by means of Revetest-CSEM. The authors demonstrated the significant influence of the presence of titanium ions (Ti+), in the vacuum arc deposition process, on the properties of the composite nitrided layer/PVD coating. The presence of titanium ions in the technological process deteriorates adhesion of the PVD coating to the nitrided substrate, when the nitrided layer includes the compound zone. This effect was not observed for a CrN coating deposited without the participation of titanium ions.