Dry sliding wear tests were performed for Ti–6Al–4V alloy on a pin-on-disc wear tester. The wear behavior of Ti–6Al–4V alloy at sliding velocities of 0.5–4m/s was studied and the tribo-oxides and their function were explored. Ti–6Al–4V alloy presented a marked variation of wear rate as a function of velocity. With the rise and fall of wear rate, Ti–6Al–4V alloy underwent the transitions of wear mechanisms from the combination of delamination wear and oxidative wear at lower speeds to delamination wear at 2.68m/s, and then to oxidative wear at 4m/s. These phenomena were attributed to the appearance and disappearance of tribo-oxides. In spite of trace or a small amount, tribo-oxides would change the wear behavior, and even wear mechanism. •The velocity caused a marked variation of wear rate in Ti–6Al–4V alloy.•Ti–6Al–4V alloy presented the transitions of wear mechanisms with velocity.•Velocity-induced tribo-oxides changed the wear behavior and mechanism.