Two series of unconventional triazine-based dendrimers with C(2) symmetry and C(3) symmetry were prepared. The newly prepared C(3)-symmetrical dendrimers were characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry, and elemental analysis. Differential scanning calorimetry, polarizing microscopy, and powder XRD showed that the C(3)-symmetrical dendrimers display columnar liquid-crystalline phases during thermal treatment, but the C(2)-symmetrical dendrimers were not observed to behave correspondingly. The molecular conformations of C(3)- and C(2)-symmetrical dendrimers were obtained by computer simulation with the MM2 model of the CaChe program in the gas phase. The simulation results reasonably explain the different mesogenicities of C(3)- and C(2)-symmetric dendrimers. This new strategy should be applicable to other types of unconventional dendrimers with rigid frameworks for displaying columnar liquid-crystalline behavior.