The electrochemical behavior of graphite has been studied using the electrochemical chain graphite/(polyethylene oxide, NaCF3SO3)/Na. The PEO-based electrolyte avoids solvent co-intercalation in the electrode material and to a certain extent, reactivity problems due to residual impurities in organic electrolytes. The amount of intercalated sodium is of the same order of magnitude as in materials prepared from reaction with sodium vapor (NaC64) but smaller than in the compounds synthesized in organic media, thus stressing the influence of solvent co-intercalation.