The tribologic properties of graphitized carbon blacks and their fluorinated derivatives are investigated as a function of the fluorination rate. Very low intrinsic friction coefficients are obtained for highly fluorinated compounds. The correlation of the tribologic results and structural investigations of the initial compounds by TEM strongly suggests that the friction mechanisms involve surface effects in the early stage of friction. Long-term tribologic experiments and Raman analyses point out an evolution of the structure and composition of the tribofilms during the friction process leading to similar friction properties of the tribofilms. Wear studies revealed that highly fluorinated derivatives appear less efficient than pristine and weakly fluorinated compounds.