In this study, dry sliding tribological properties of a TiZr-based alloy with the chemical composition Ti-20Zr-6.5Al-4V (wt.%) were tested in air and vacuum under different normal loads (10, 20, and 30N) at various sliding velocities. Results showed that the coefficient of friction in air was lower than that in vacuum, whereas the wear volume at sliding velocity presented an opposite trend. The surfaces and cross-sectional morphology of wear scar on the TiZrAlV alloy was analyzed through scanning electron microscopy to determine the wear mechanisms. The observations showed that abrasive wear and delamination wear were dominant in air. In vacuum, the main wear mechanism changed from slightly abrasive and adhesive wear to severe adhesive wear and delamination wear as the normal load increased. Wear mechanism maps were also constructed and compared. The comparison showed that severe wear (including delamination wear) was prevalent in air.