Tool wear phenomena during the machining of titanium alloys are very complex. Severe adhesive interaction at the tool chip interface, especially at low cutting speeds, leads to intensive Built Up Edge (BUE) formation. Additionally, a high cutting temperature causes rapid wear in the carbide inserts due to the low thermal conductivity of titanium alloys. The current research studies the effect of AlTiN and CrN PVD coatings deposited on cutting tools during the rough turning of a Ti6Al4V alloy with severe BUE formation. Tool wear characteristics were evaluated in detail using a Scanning Electron Microscope (SEM) and volumetric wear measurements. Chip morphology analysis was conducted to assess the in situ tribological performance of the coatings. A high temperature–heavy load tribometer that mimics machining conditions was used to analyze the frictional behavior of the coatings. The micromechanical properties of the coatings were also investigated to gain a better understanding of the coating performance. It was demonstrated that the CrN coating possess unique micromechanical properties and tribological adaptive characteristics that minimize BUE formation and significantly improve tool performance during the machining of the Ti6Al4V alloy.