In recent years, concern has been raised about the charge fluctuation of the superconducting transition in the loosely dimerized molecular conductors. Not only the observation of the charge fluctuation is of considerably important but also the understanding of the mechanism of the fluctuation. We have observed degree of charge fluctuation of several b 00 -type ET salts. The b 00 -type ET salt is one of the best model compounds because the direction of the largest inter-site Coulomb interaction is perpendicular to that of the largest transfer integral. This structural property allows us to examine the role of inter-site Coulomb interaction from the viewpoint of the inter-molecular distance. The difference in the molecular charges between the charge rich site and the charge poor sites, Dr, is correlated with the conducting behavior; the superconducting materials have the small but finite Dr, whereas Dr of the insulating (metallic) materials is large (almost zero). After the analysis of the configuration in the intermolecular distances, we have found that the degree of fluctuation, Dr, is attributed to the number of the most stable charge distribution(s), N S , and the number of the energy levels of the allowed charge distribution, N A . The superconducting materials belong to the condition of N S Z 2 and N A Z 2. Indeed, this condition contributes to the fluctuation of the molecular charges.