Frictional heating is common during the dry sliding of polymers against steel, which further makes it complex to understand the friction and wear performance of polymers at high temperature. Towards the goal of addressing the tribological response of polymers to such combined temperatures, the counter steel was heated crossing the glass transition (150 °C) of polyetheretherketone (PEEK), and tribological tests were conducted during temperature ramping or at constant counterbody temperatures. With increasing temperature, different friction responses were revealed depending on the variation manner of temperature (sliding during ramping or at controlled counterbody temperature). Even so, counterbody temperature around PEEK’s glass transition defined a transition, from which distinct friction and wear of PEEK was exhibited. Based on real-time analysis of temperature in the counterbody and PEEK near to the sliding interface, the completion between frictional and external heating is discussed. In combination with worn surface characterization, this also helped understand the mechanisms behind such kind of tribological response to temperatures.