For the first time, blends of melt processable polytetrafluoroethylene (MP PTFE) with polyetheretherketone (PEEK) in the MP PTFE/PEEK ratio of 100/0, 80/20, 50/50, 20/80, and 0/100 w/w were prepared and characterized. MP PTFE/PEEK blends are attractive materials due to the combination of low coefficient of friction and universal chemical resistance of MP PTFE with good wear resistance and mechanical strength of PEEK while maintaining high thermal stability of both. Miscibility, phase morphology, and mechanical properties of the new MP PTFE/PEEK blends were investigated. To improve their end-use properties, an attempt of reactive compounding with the electron beam irradiated MP PTFE (e-beam MP PTFE) was made. The reactive compounding was done in two steps, that is, the preparation of a masterbatch (MB) consisting of e-beam MP PTFE/PEEK (50/50 w/w) and subsequent melt blending of MP PTFE/PEEK with varying concentrations of MB. The e-beam irradiation of MP PTFE carried out in air atmosphere and at room temperature with a dose of 50 kGy results in its chain scission associated with formation of COF and COOH functional groups. Such modified MP PTFE can be used to compatibilize MP PTFE/PEEK blends. Reactive compatibilized blends exhibit improved phase morphology and mechanical properties. Especially for MP PTFE/PEEK 50/50 blends, a great improvement of almost 250% in strain at break, 40% in stress at break, and more than 600% in toughness was achieved. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013