We demonstrate the field-effect transistors (FETs) made of cyclo[8]pyrrole thin films prepared by the Langmuir-Blodgett (LB) method. The cyclo[8]pyrrole molecule possesses a 30-pi-electron system and narrower highest-occupied molecular orbital-lowest-unoccupied molecular orbital energy gap (0.63 eV), forms a stable, reproducible monolayer at the air-water interface, and transfers onto a substrate with a nearly unity transfer ratio and face-to-face configuration due to its strong pi-pi interaction. The LB films are uniform characterized by atomic force microscopy and in ordered form confirmed by X-ray diffraction. The FET exhibited high performances with one of the highest hole mobilities (0.68 cm(2) V-1 s(-1)) for thin-film transistors and a high on/off ratio, implying a promising material in the FET family.