Tribological behaviours of Ti-6Al-4V alloy pins sliding against GCr15 steel discs over a range of contact pressures (0.33-1.33 MPa) and sliding velocities (30-70 m/s) were investigated using a pin-on-disc tribometer under unlubricated conditions. The wear mechanisms and the wear transition were analyzed based on examinations of worn surfaces using SEM, EDS and XRD. When the velocity increases, the friction coefficient and the wear rate of the Ti-6Al-4V alloy show typical transition features, namely, the critical values of sliding velocities for 0.33 and 0.67 MPa are 60 and 40 m/s, respectively. The experimental results reveal that the tribological behaviours of Ti-6Al-4V alloys are controlled by the thermal-mechanical effects, which connects with the friction heat and hard particles of the pairs. A tribolayer containing mainly Ti oxides and V oxides is formed on the worn surface of Ti-6Al-4V alloy.