Multi-walled carbon nanotubes (MWNTs) were oxyfluorinated at several different temperatures. The results indicated that graphitic carbon was the major carbon functional component on the MWNT surfaces and other functional groups, such as C–O, C=O, HO–C=O, C–Fx, were also present after oxyfluorination. The changes of surface properties of oxyfluorinated MWNTs were investigated using FT-IR, EDS and XRD. From the surface analysis, it was found that surface fluorine and oxygen contents increased with increasing oxyfluorination temperature and showed a maximum value at 100 °C. Consequently, it was found that optimal treatment temperature was 100 °C for the best electro activity of Pt/MWNT-100 catalyst and the oxyfluorinated Pt/MWNTs possessed the better electrochemical properties than the pristine Pt/MWNTs.