The dynamics of friction and wear of a contact pair consisting of 40CrNiMoA steel/Si3N4 ball were determined at 400 and 600 °C respectively with a variable of sliding duration in air. The results showed that, a friction instability primarily occurred at the initially running-in period and an exponential decrease in the specific wear rate appeared at both temperatures. The temperature exerts greater influence on the spontaneous formation of tribo-oxide layer on the rubbing contact, and the deleterious effects of wear at 600 °C. Friction-induced hardening accounted for improved wear resistance behavior along with the sliding extending. The influence of temperature on structural alteration and elemental migration at the rubbing surface was further discussed on the basis of mechanics of tribo-induced layer.