Organic semiconducting single crystals (OSSCs) are ideal candidates for the construction of high-performance optoelectronic devices/circuits and a great platform for fundamental research due to their long-range order, absence of grain boundaries, and extremely low defect density. Impressive improvements have recently been made in organic optoelectronics: the charge-carrier mobility is now over 10 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> and the fluorescence efficiency reaches 90% for many OSSCs. Moreover, high mobility and strong emission can be integrated into a single OSSC, for example, showing a mobility of up to 34 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> and a photoluminescence yield of 41.2%. These achievements are attributed to the rational design and synthesis of organic semiconductors as well as improvements in preparation technology for crystals, which accelerate the application of OSSCs in devices and circuits, such as organic field-effect transistors, organic photodetectors, organic photovoltaics, organic light-emitting diodes, organic light-emitting transistors, and even electrically pumped organic lasers. In this context, an overview of these fantastic advancements in terms of the fundamental insights into developing high-performance organic semiconductors, efficient strategies for yielding desirable high-quality OSSCs, and their applications in optoelectronic devices and circuits is presented. Finally, an overview of the development of OSSCs along with current challenges and future research directions is provided.