Thermal expansion mismatch stresses may be a reason for premature failure of sealing and bearing components made of polymer composites that are rubbed against metallic surfaces at elevated temperatures. It is of particular importance for polymer matrix composites loaded with anti-friction inclusions of polytetrafluoroethylene (PTFE) that possesses high coefficient of thermal expansion. In this regard, a study was undertaken to elucidate the effect of the thermal mismatch on wear and friction of amorphous polyetherimide (PEI) matrix loaded with either polytetrafluoroethylene (PTFE) particles (i) or PTFE particles covered with negative thermal expansion zirconium tungstate (ZT) α-ZrW2O8 (ii) at temperatures 23 °C, 120 °C and 180 °C. The ball-on-disk testing scheme was used according to standard with AISI 52100 steel balls rubbed against a polymer composite disks at normal force P = 5 N and sliding velocity V = 0.3 m/s. The PEI/PTFE/ZT composite demonstrated a tendency for wear rate (WR) reduction in sliding at 120 °C and 180 °C as compared to corresponding WR enhancement on the PEI/PTFE. The rationale is provided that the ZT additive effectively reduced thermal expansion of the PTFE in the PEI matrix and thus improved wear resistance of the composite. New thermal expansion-controlled wear and friction instability mechanism has been proposed and discussed.