[en] The introduction of a methyl group into ethylenedioxytetrathiafulvalene (EDO-TTF) greatly modified the molecular character as a component for the conducting complexes. While the pristine EDO-TTF almost exclusively formed head-to-tail type overlapping with the neighboring donor molecules in the complexes, the methyl substituted compound, MeEDO-TTF, showed both the head-to-head and head-to-tail overlapping patterns. In the former case, the donor molecules interacted with each other in a two-dimensional fashion to provide stable metals along with the charge-ordered complex which exhibited semiconductor-semiconductor first-order transition just above room temperature. The overlapping pattern of MeEDO-TTF directly corresponded to the electronic structure of the complex. In the case of head-to-tail packing patterns, the charge carriers were delocalized only in a quasi-one-dimensional column or in a multimer composed of the donor molecules. The comparison of the intermolecular overlap integrals calculated in the extended Hueckel level suggested that at least the magnitude of ca. 10x10^-3 is needed for the infinite chain or network of the conducting component molecules to exhibit metallic nature.