Abstract Poly(ether‐ether‐ketone) (PEEK) is a key structural material in lightweight robots, yet its poor self‐lubricity limits use in moving components. This study develops PEEK‐based composites incorporating poly(tetra‐fluoroethylene) (PTFE) as the lubricating phase and Ti 3 C 2 T x MXene as transfer film mediator is designed and fabricated via hot‐press sintering. Their mechanical properties are studied via a compressive test, and their tribological performances are probed upon sliding against the ZrO 2 ball with a linear reciprocating ball‐on‐plane configuration. By synergistically regulating the content of PTFE and MXene, the threshold content of PTFE and MXene for achieving an ultra‐low friction can be obtained, which strengthens the composites and thus contributes to ultra‐low wear. At an optimal PTFE content of 10 wt.%, MXene addition doubles the engineering strain, accompanied by an 11% increase in compressive strength. Meanwhile, the increased content of Ti 3 C 2 T x continuously reduces the coefficient of friction to 0.060 ± 0.001, which is 26.83% lower than that of the composite without MXene, while keeping the wear rate at a low level of 10 −6 mm 3 N −1 ·m −1 . According to the molecular dynamics simulation, the excellent anti‐friction and anti‐wear performance can be attributed to the controlled release of PTFE by Ti 3 C 2 T x MXene, which originates from their strong interfacial bonding.