The induction of the columnar phase is described in which intrinsically crystalline 1,4,6,9-tetraacyloxypyrenes have been mixed with tetranitrofluorenone, TeNF, as an electron acceptor. The pyrene derivative with linear nonyl chains, PC9, has not shown any mesophases using trinitrofluorenone, suggesting that stronger charge transfer interaction is favored by TeNF. The shape of the substituents works to control the mesophase type: the mixture of PC9 and TeNF has formed a rectangular columnar phase, and a hexagonal columnar phase is attained by rounder derivatives bearing branched side chains.