The synthesis and characterization of fluorinated carbon nanotubes have been carried out under an inert gas containing fluorine. All of the samples have been characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance ((13)C and (19)F ss-NMR) and transmission electron microscopy (TEM) techniques. The comparison of the effects of various experimental parameters on the structure of fluorinated materials allows the disclosure of the fluorination mechanism. It is shown that fluorine was intercalated into the outer part of the carbon nanotubes initially where graphene layers were coaxial within a distance of 0.60 nm. In contrast, the inner part of the carbon nanotubes was not intercalated. The electrochemical performance such as discharge capacity as a cathode for a primary lithium battery has also been investigated. The samples with a F/C ratio of 0.75 exhibited the best performance, namely high energy and power densities. The highest specific energy density and specific power density were 1147 Wh kg(-1) and 8998 W kg(-1), respectively, at a current density of 4 A g(-1).