High-performance polymers (HPPs) are increasingly used in different industrial machinery components, particularly for rubbing parts that demand reliable and durable operation at extreme sliding conditions such as elevated temperature environments, where the use of conventional lubricants is not feasible. The current study investigates the role of environmental temperature on the tribological properties of three advanced HPPs, namely aromatic thermosetting copolyester (ATSP), polyimide (PI), and polyether ether ketone (PEEK) based polymer composites. Tribological experiments were carried out at different environmental temperatures from room temperature up to 300 C, and under dry sliding conditions. Specific attention was given to the role of temperature on the development of transfer films and its subsequent effect on the tribological performance. The ATSP composite was recommended as the best performing material, based on the overall tribological performance at all examined operating temperatures.