The initial point for the development of chemically coupled PTFE-materials is represented by the chemically coupled PTFE-PA compounds, which exhibit extraordinary wear resistant values and a low coefficient of friction. For a chemical coupling of PTFE with composition rubber, a further modification of the irradiated PTFE with other functional groups can be achieved using different methods which is presented here. Irradiated PTFE powders possess persistent radicals, which can be used for graft copolymerisation with different monomers as well as for a direct coupling with olefinic unsaturated matrix polymers such as SBS, ABS, NBR, EPDM etc. during the reactive extrusion process. Regarding these results, developments of novel materials for high performance tribological applications can be realised by simple and competitive irradiation and extrusion processes.