Many organic conducting materials are represented by the charge transfer (CT) complexes of tetrathiafulvalene (TTF) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), which show high conductivity at room temperature. CT complexes of TTF and TCNQ each form columnar structures in crystals that enable the application of CT complexes in the formation of one-dimensional nanostructures such as nanowires and nanorods. Crown ethers units can also be used to support the preparation of self-assembled one-dimensional structures. In this study, we reported that the structures and electrical properties composed of TTF derivative (TTF-ER) and CT complexes composed of (TTF-ER)(TCNQ), (TTF-ER)(F2TCNQ) and (TTF-ER)(F4TCNQ). TTF-ER and the CT complexes organized one-dimensional structures on solid substrate, and in particular, TTF-ER formed high oriented nano-branched structures. In UV–vis and IR spectra, the CT complexes has conductivity similar to that of semiconductors, the electrical conductivities of (TTF-ER)(F2TCNQ) and (TTF-ER)(F4TCNQ) at room temperature were found to be 1.2 × 10−5 and 1.4 × 10−5 S cm−1, respectively.