Three novel gallic–perylene–gallic trimers 7, 8 and 9 were synthesized by reacting gallic amino derivatives 3, 4 or 6 with perylene tetracarboxylic anhydride in yields of 75%, 78% and 80%, respectively. Compounds 7 and 8 with soft bridging chains exhibit columnar mesophase at room temperature, but compound 9 with a rigid bridging chain exhibits no mesophase.