The molecular aggregations in liquid crystalline 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes (PTAC, n = 4, 8, 12), which were prepared via an innovative route of a simple phase transfer catalysis method, were investigated through UV/Vis absorption, XRD, DSC, and polarization microscopy. Some interesting aggregate behaviors caused by the length of attached alkyl chains were observed. It was found that it was easier for PTAC derivatives with shorter alkyl chain to form crystal films and liquid crystals. (c) 2005 Elsevier B.V. All rights reserved.