Over the last decade, research on high-temperature tribological characteristics of Ti6Al4V alloy has been gathered significant interest due to their sustainable properties in high-temperature applications. Adhesion and abrasion have been identified as the most prevalent wear mechanism in the tribological system operated under high temperatures. Hence, the present study aimed to investigate the high-temperature wear behavior of titanium alloys under a vacuum environment and various operating conditions in order to explore the formation of no-oxide tribo layers and the governing wear mechanisms. The transition of materials from both the worn surfaces (Pin and Disc) has been demonstrated. The microstructural characteristics of the worn surfaces and cross-sections revealed the formation of no-oxide tribo-layers which significantly influenced the wear rates as well as governed wear mechanisms. Due to the formation of no-oxide layers, the coefficient of friction was observed to increase with increasing the temperature and load.