Triphenylene-containing polyacetylenes with different lengths of alkoxy chains on the pendants are designed and synthesized {-[HC=C(CH₂)₈COOC₁₈H₆(OR)₅]_n-, R = C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₅, C₈H_17, and C₉H₁₉}. The polymers are prepared in high yields (up to 80%) by [Rh(nbd)Cl]₂ catalyst (nbd = 2,5-norborndiene) in organic solvents mixed with triethylamine. The structures and properties of the polymers are characterized by IR, POM, TGA and DSC analyses. All the polymers are thermally stable (>350 ^oC). The polymers show mesomorphic textures at high temperatures, suggesting the formation of columnar liquid crystal phase. With an increase in the alkoxy chain length, the order of the packing arrangement of the mesogenic pendants increases, whereas the transition temperature decreases.