The tribological characteristics of a glass‐forming alloy, Zr52.5Cu17.9Ni14.6Al10.0Ti5.0, in atomic percent (at.%, Vit 105), with different microstructural states have been investigated. Friction and wear studies were conducted using a ball‐on‐flat reciprocating sliding apparatus against an AISI E52100 bearing steel under dry condition. The observed wear resistance in an ascending order is: the deformed, creep‐tested, and as‐cast states. Wear analyses suggested that the wear processes of glass‐forming alloys involved abrasion, adhesion, and oxidation. The differences in hardness, free volume, and brittleness in different states significantly affected the friction and wear behaviors of the glass‐forming alloys.