The aim of this study was to characterized of the nanostructured, multilayer coatings (CrN/Cr)x8 on Ti6Al4V titanium alloy obtained using vacuum-arc surface engineering method. The investigations were focused on microstructure, chemical and phase composition and crystallographic orientation of the CrN and Cr sub-layers. The special attention has been paid on the transition layer between CrN and Cr phases. This layer, several tens of nanometer in thickness, ensures good coherence, adhesion, wear and corrosion resistance of the CrN/Cr multilayer coatings. The samples for the observation have been prepared using Focus Ion Beam (Hitachi FB2100) microscope followed by low-energy argon ion polishing using Gentle Mill Technoorg Linda to achieve desired film thickness and artifact- and damage-free surface. The microstructure investigations have been performed using scanning electron microscope SEM/STEM Hitachi 5500, transmission electron microscope JEOL 1200EX and Cs-corrected dedicated STEM Hitachi HD2700. The thickness of the nanostructure, multilayer coating CrN/Cr was of 8,5 µm. These composite coatings consist of 8 sub-layers of CrN 700 nm thick and 8 sub-layers of Cr 400 nm in thickness. The performed investigations will help to understand the structure – properties relationship, which can be crucial in designing and modeling nanostructure, multilayer coatings CrN/Cr.