Well-aligned organic single-crystalline semiconductors are essential for practical applications in electronic devices. Here, we demonstrated dioctylbenzothienobenzothiophene (C8-BTBT) single crystals via an ultrasound concussion-assisted solution-processing method. Organic crystalline semiconductors with a fence-like shape were achieved, where rod-like crystals were joined together along a crystalline backbone up to millimeter length, which can allow the deposited crystals to combine the features of well-aligned orientation and desirable deposition. Organic field-effect transistors (OFETs) were fabricated using the C8-BTBT single crystals, yielding a high field-effect hole mobility up to 6.0 cm2 V−1 s−1. Therefore, the ultrasound-assisted solution process can provide a general guide for the integration of functional materials into high performance devices.