Although perylene crystals have been known to show both dimeric (α) and monomeric (β) phases, to date only the stable α-crystals have been obtained under conventional conditions. Here, we propose a procedure for the selective growth of β-phase perylene crystals, in which a saturated toluene solution at 350 K was cooled to 298 K with a high cooling rate (-30K/min). The sizes of β-phase crystals obtained were in the order of 100 μm. Copyright © 2007 The Chemical Society of Japan.