A liquid-crystalline (LC) phenylterthiophene derivative, which exhibited an ordered smectic phase at room temperature, was purified by vacuum sublimation under a flow of nitrogen. During the sublimation process, thin plates with sizes of 1 mm grew on the surface of the vacuum tube. The crystals exhibited the same X-ray diffraction patterns as the ordered smectic phase of the LC state that was formed through a conventional recrystallization process by using organic solvents. Because of the removal of chemical impurities, the hole mobility in the ordered smectic phase of the vacuum-grown thin plates increased to 1.2×10−1 cm2 V−1 s−1 at room temperature, whereas that of the LC precipitates was 7×10−2 cm2 V−1 s−1. The hole mobility in the ordered smectic phase of the vacuum-sublimated sample was temperature-independent between 400 and 220 K. The electric-field dependence of the hole mobility was also very small within this temperature range. The temperature dependence of hole mobility was well-described by the Hoesterey–Letson model. The hole-transport characteristics indicate that band-like conduction affected by the localized states, rather than a charge-carrier-hopping mechanism, is a valid mechanism for hole transport in an ordered smectic phase.