Using galvanostatic discharges, the electrochemical properties of fluorinated carbon nanofibers (CNF) have been investigated. Several methods of fluorination are compared, (i) direct process using a flux of pure molecular fluorine F2 (dynamic process), (ii) controlled fluorination using atomic fluorine released continuously by the thermal decomposition of a solid fluorinating agent (TbF4), and (iii) static fluorination by the filling of a closed reactor with undiluted molecular fluorine as reactive gas. Electrochemical performances of the resulting materials are compared highlighting significant improvement using the static method. The discharge potential increases from 2.27 V (vs. Li+/Li°) for materials obtained by the direct route to a medium 2.40 V by the static route resulting from a two steps discharge mechanism. Owing to a complete characterization of each fluorinated materials by X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM), the increased average potential of fluorinated sample through the static way has been explained by the peculiar distribution of fluorine and carbon sites in the nanomaterial. Then, in order to understand the two steps discharge mechanism of the latter material, its discharge mechanism through galvanostatic measurements at different depths of discharge has been investigated in different electrolytes. The discharged materials have been studied owing to 19F MAS NMR, XRD and scanning electron microscopy characterizations. The texture and cristallinity of lithium fluoride particles are key parameters acting on the ionic diffusion of Li+ and F− ions and as a consequence on the electrochemical performances. Its high solubility in EC/PC/3DMC solvent mixture prevents from overvoltage phenomenon occurring during the discharge of fluorinated carbon nanofibers in primary lithium battery.