Tribological applications of polytetrafluoroethylene (PTFE) are often limited by technological complexity to overcome its poor wear resistance. Here, a PTFE/polyetheretherketone (PEEK) heterolayer (HL) was proposed and evaluated as a new solid lubrication solution. Pin-on-disk tribometry found the lowest friction coefficient (μ) of 0.031 and ultralow wear for the PEEK/HL under typical conditions. The friction coefficient of the HL surpasses those of the state-of-the-art polymeric coatings/composites by at least 200%, and approaches that of highly lubricated interfaces. Mechanistic investigations revealed multi-length physical and chemical heterogeneity of the HL that best facilitates a tribofilm with high subsurface stability and surface instability. The technological simplicity and robustness of the HL’s high lubricity make it a promising new type of solid lubrication toward greater reliability and longevity.