In the present work, surface engineering of Ti6Al4V, produced via selective laser melting parts was carried out with the aim of investigating how surface features of substrate may improve the coupling with AlTiN coatings deposited by Physical Vapor Deposition 2 reactive High-Power Impulse Magnetron Sputtering. In particular, the work highlighted how vacuum thermal treatments at 800°C induced peculiar mesoscale morphology and surface chemical modifications of the Ti6Al4V, which contributed to improve the adhesion of the deposited AlTiN thin films. Chemical composition, crystallographic structure, and surface properties of both substrates and coatings were analyzed by Field Emission Scanning Electron Microscopy (equipped with Energy Dispersive Spectroscopy), Atomic Force Microscopy, X-ray Photoelectron Spectroscopy, X-Ray diffraction, nanoindentation, and scratch test measurements.