AbstractSince the macroscopic properties of materials are relevant to their micro structure, the detection of microscopic defects or their changes in size and concentration is an interesting topic in materials science. The positron annihilation lifetime (PAL) method used here is established as a unique technique that can provide information about the size and concentration of free volume holes directly without significantly intervening in the bulk properties of the specimens. To our knowledge, this is the first time that PAL techniques have been used to study the wear mechanism of macromolecular tribomaterials. Here we present the results of a study in which the correlation between the fretting wear behaviour of polytetrafluorethylene (PTFE) and the changes in its free volume size and concentration in amorphous‐crystal interface regions was found to be δω =A.δτ3, where δω is the wear loss of PTFE under fretting wear conditions, A is a constant, and δτ3represents the relative change in the third lifetime components after the friction test. The results indicate that fretting mainly influences the characteristics of atomic‐scale free volume holes in the amorphous‐crystal region in PTFE, and under high‐load fretting wear conditions the ductile polymer PTFE possesses a self‐curing function for its defect‐free