Abstract Two kinds of graphite fluorides, (CF) n and (C 2F) n , are prepared by the reaction of elemental fluorine with carbon materials at temperatures of 350–640°C. (CF) n has a chair-type structure different from that of (C 2F) n , which is a so-called second stage compound having C-C bond perpendicular to the carbon network. The heats of immersion of (CF) n are smaller than those of Teflon and Graphon, and that of (C 2F) n is nearly equal to that of Teflon. The surface energy of (CF) n evaluated from contact angle measurement was about 6 erg/cm 2. The electrochemical study of (CF) n and (C 2F) n revealed that open circuit voltage of (CF) n was 0.2 V higher than that of (CF) n , and the overvoltage observed on galvanostatic discharge was also lowered by 0.4 V. Discharge reaction is controlled by the diffusion process of a Li + ion through the interlayer spacing of graphite fluoride.