Abstract: New thiophene diaminotriazine bearing two alkyl chains in the thiophene ring has been synthesized via Kumada coupling reaction as the key step.Its supramolecular liquid crystalline complex with semiperfluorinated benzoic acids has been prepared and the structure and mesophase characterization of this complex were investigated with infrared spectra and POM.Columnar mesophase was found in this complex.It is presumed that the hydrogen bonding between the diaminotriazine and benzoic acid leads to discrete dimeric supermolecule and enhances the polarity of the core region of the dimeric supermolecule;simultaneously, an increased intramolecular polarity contrast caused by semiperfluorinated chains favors a microsegregation,leading to the fromation of the columnar phase.