The sliding friction and wear behaviours of Ti-6Al-4V alloy were investigated under dry sliding wear conditions. The wear tests were carried out on a pin-disc tribometer at sliding speeds from 30 m/s to 70 m/s and at contact pressure ranging from 0.33 MPa to 1.33 MPa. Pins of the Ti-6Al-4V alloy are used in both solution treated and aged conditions. The objective of the study is to understand the influence of thermo-mechanical mixed layers (TMML), which form on the surface of the worn material during the course of the wear test, on the friction and wear behaviour. Detailed characterization of the TMML was carried out using SEM, EDS and micro-hardness testing in order to understand the influence of test velocity and contact pressure on the composition, hardness and thickness of the TMML formed. The influence of the TMML on the friction and wear behaviour was also studied. On the basis of the above characterization, it was demonstrated that the observed friction and wear behaviour of Ti-6Al-4V alloy can be best understood in terms of the formation and fracture rate of the TMML rather than the bulk properties of the material.