Click chemistry between alkynes and azides high efficiently produces triazoles and would be a convenient tool for synthesis of discotic liquid crystal dimers, oligomers and polymers. In this report, triphenylenes containing terminal alkynes and azides were prepared, and the cycloaddition reaction (click chemistry) between them catalyzed by CuI-Et(3)N in toluene produced discotic liquid crystal dimers in high yield and good selectivity. The dimers and intermediates have been fully characterized by (1)H NMR and high resolution MS. Polarized optical microscopy (POM) and differential scanning calorimetry (DSC) results show the dimers possess columnar mesophase in wide temperature range from very low temperature. The triazole moiety in the dimer can act as electron and hydrogen bond acceptor, and ionic forming part, rich chemical and physical properties can be expected from these new structure discotic dimers.