ConspectusThe design, synthesis, and characterization of organic semiconductors applicable to organic electronic devices, such as organic field-effect transistors (OFETs) and organic photovoltaics (OPVs), had been one of the most important topics in materials chemistry in the past decade. Among the vast number of materials developed, much expectation had been placed on thienoacenes, which are rigid and planar structures formed by fusing thiophenes and other aromatic rings, as a promising candidate for organic semiconductors for high-performance OFETs. However, the thienoacenes examined as an active material in OFETs in the 1990s afforded OFETs with only moderate hole mobilities (approximately 0.1 cm2 V-1 s-1). We speculated that this was due to the sulfur atoms in the thienoacenes, which hardly contributed to the intermolecular orbital overlap in the solid state. On the other hand, we have focused on other types of thienoacenes, such as benzothieno[3,2-b]benzothiophene (BTBT), which seem to have appropriate HOMO spatial distribution for effective intermolecular orbital overlap. In fact, BTBT derivatives and their related materials, including dinaphtho[2,3-b: 2′,3′-f]thieno[3,2-b]thiophene (DNTT), have turned out to be superior organic semiconductors, affording OFETs with very high mobilities. To illustrate some examples, we have developed 2,7-diphenyl BTBT (DPh-BTBT) that yields vapor-deposited OFETs having mobilities of up to 2.0 cm2 V-1 s-1 under ambient conditions, highly soluble dialkyl-BTBTs (Cn-BTBTs) that afford solution-processed OFETs with mobilities higher than 1.0 cm2 V-1 s-1, and DNTT and its derivatives that yield OFETs with even higher mobilities (>3.0 cm2 V-1 s-1) and stability under ambient conditions. Such high performances are rationalized by their solid-state electronic structures that are calculated based on their packing structures: the large intermolecular orbital overlap and the isotropic two-dimensional electronic structure are the key regardless of the molecular size and substituents on the BTBT and its related thienoacene cores. Along with the discovery of such attracting performances, versatile and practical methods for the synthesis of BTBT and its derivatives, and the π-extended derivatives including DNTT, dianthra[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DATT), and the thienoacenes with two thieno[3,2-b]thiophene moieties, have been developed. In addition, the materials have been recently utilized in sophisticated devices and circuits, including all-printed transistor arrays, flexible circuits on ultrathin plastic substrates, and biomedical applications, underscoring their promise as practical semiconductors for electronic device applications. These exciting results of the present BTBT-based materials are expected to open doors to new horizons of organic semiconductors in terms of practical application and the design and synthesis of far more superior materials.