Abstract: A review with 134 references on the molecular and structural characteristics of PTFE, transfer behavior and its effect on tribologi-cal performance of PTFE and composites. Based on literature survey, influencing factors about formation of the transferred film of PTFE, fundamental of interaction between the transferred film and substrates, observation of detaching the transferred film from substrate, forming debris and the effect of crystallinity on wear and friction of PTFE are discussed in detail. Tribological performance of PTFE-based composites filled by inorganic and metallic powders, various fibres and organic materials are also reviewed.