In this paper, we studied the effect of carbon fibers on the performance properties of polymer composites based on polytetrafluoroethylene. It was shown that the introduction of PTFE carbon fibers significantly improved tribological and mechanical properties of the composite. The correlation between the performance properties and supramolecular structure was found. Initial lamellar structure of the polymer became less in size without significant changes in morphology when filled. Such process was accompanied by the increase of crystalline regions number and the crystallinity degree of composite. Structural studies have shown that materials with more densely packed and highly crystalline structure have increased mechanical and tribological properties. The developed materials can be used in friction units of machines and devices, where the use of lubricants is not acceptable or restricted.