Discotic liquid crystalline polymers bearing alkoxy-substituted triphenylene moieties in the side-chain were synthesized by ring-opening metathesis polymerization using a well-defined ruthenium initiator. To elucidate the effect of backbone flexibility on the mesomorphism, norbornene and cyclobutene monomers containing triphenylene moieties were synthesized, which yielded the relatively rigid poly(norbornene)s and the more flexible poly(butadiene)s, respectively, after polymerization. To further increase the backbone flexibility, the poly(butadiene)s were hydrogenated using Crabtree’s catalyst to yield triphenylene-substituted poly(butane)s. The mesomorphic behavior of the polymers has been investigated by differential scanning calorimetry (DSC) and powder diffraction X-ray scattering (wide angle X-ray scattering, WAXS). All polymers bearing a 2,3,6,7,19-pentakis(decyloxy)triphenylene-based mesogenic unit exhibit enantiotropic discotic hexagonal mesophases, while the pentoxy analogues do not display liquid crystalline behavior. No effect of backbone rigidity on the mesomorphism could be detected.