Previously, we reported that bis[1]benzothieno[2,3-d:2′,3′-d′]naphtho[2,3-b:6,7-b′]dithiophene (BBTNDT1) with two fused BTBT substructures gave high hole mobility up to 5.6 cm2/Vs and had a two-dimentionally interactive herringbone packing structure (Ref. 1). In this work, we have newly synthesized two structural isomers of BBTNDT1, bis[1]benzothieno[2,3-d:2′,3′-d′]naphtho[1,2-b:5,6-b′]dithiophene (BBTNDT3) and bis[1]benzothieno[2,3-d:2′,3′-d′]naphtho[2,1-b:6,5-b′]dithiophene (BBTNDT4) and investigated the properties of three BBTNDT isomers. The ionization potentials of BBTNDT3 and BBTNDT4 were of -5.6 eV, which was lower than that of BBTNDT1 (-5.1 eV), clearly indicating their difference in electronic structures. We have also investigated their OFET characteristics using the bottom gate, top contact device structure on Si/SiO2 substrates. Compared with BBTNDT1, BBTNDT3 and BBTNDT4 showed relatively low mobility of 0.44 and 0.044 cm2/Vs, respectively. This might be caused by the difference in their packing structures in thin film. From X-ray diffraction of thin films, BBTNDT3 was considered to have an edge-on orientation with herringbone packing structure on the substrate. However, the crystallinity was low, as evidenced by sub peak observed in its out-of-plane XRD pattern. On the other hand, the single crystal X-ray analysis of BBTNDT4 revealed that it had one-dimentionally pi-stacked structure. This anisotropic crystal structure of BBTNDT4 seems to limit its carrier transporting in thin film. Together with the parent compounds, we will also report the synthesis, properties, and OFET characteristics of substituted BBTNDT derivatives. (Ref. 1) T. Mori, et al., JACS, 2013, 135, 13900.