Among the polycyclic aromatic hydrocarbons, although perylene is commercially available and possesses higher solubility and stability than the others, its thin-film structures and organic field-effect transistor (OFET) performances have been rarely explored. To understand its potential as an active material in OFETs, the polymorphic behaviors, packing structures, and OFET characteristics of perylene were carefully examined. The well-oriented crystal arrays of perylene prepared via droplet-pinned crystallization delivered the highest hole mobility among the reported perylene OFETs. Fluorescence microscope, electron diffraction, and lattice modeling results confirm the polymorphic behavior of perylene in the solution-processed crystal arrays and its influences on the OFET performances. The concentration-sensitive and temperature-sensitive polymorphic behavior of perylene make processing conditions crucial in the preparation of pure-phase crystal arrays. The results show the great potential of perylene as an active material in low-cost and high-performance OFETs. Moreover, the knowledge regarding the polymorphic behavior of perylene provides opportunity for the further optimization of perylene-based OFETs.