Ti1-xAlxN coating is formed by replacing some Ti atoms in TiN with Al atoms, and their properties are closely related to Al content (0 < x < 1). Recently, Ti1-xAlxN-coated tools have been widely used in the machining of Ti-6Al-4V alloy. In this paper, the hard-to-machine material Ti-6Al-4V alloy is used as the study material. Ti1-xAlxN-coated tools are used for milling experiments. The evolution of the wear form and the wear mechanism of Ti1-xAlxN-coated tools are studied, and the influence of Al content (x = 0.52, 0.62) and cutting speed on tool wear are analyzed. The results show that the wear on the rake face changes from the initial adhesion and micro-chipping to coating delamination and chipping. Wear on the flank face varies from the initial adhesion and grooves to boundary wear, build-up layer, and ablation. The main wear mechanisms of Ti1-xAlxN-coated tools are dominated by adhesion, diffusion, and oxidation wear. Ti0.48Al0.52N coating protects the tool well and extends its service life.