An experimental exploration research and comparison of the residual stress state between micro- and meso-milling processes with a ball-end mill on the Ti-6Al-4V titanium alloy were carried out. The residual stress state was analyzed based on the chip formation process according to the lead and tilt angles of the tool axis in relation to the normal vector to the surface. A novel idea was proposed to study the characteristic kinematics of a five-axis machining process, in a three-axis vertical machining center. When using the up-milling cutting strategy, it was found the defect of smeared/adhered material to the surface occurs in both the micro- and meso-milling levels, associated with the build-up edge and build-up layer phenomenon. The stress tensor of the surface was obtained using the X-ray diffraction technique. The down-milling cutting strategy produced the best surface finish and higher compressive residual stresses. Higher compressive residual stresses were found in the feed direction than in the cross-feed direction. The micro-milling process produced higher compressive residual stresses than those observed in the meso-milling process.