ABSTRACTTwo series of discotic dimers T3Dn and T5Dn based on hexapropoxytriphenylene (HAT3) and hexapentyloxytriphenylene(HAT5), respectively, with polymethylene linkage O(CH2)nO (n = 3–12) have been synthesised. Their mesomorphism was investigated by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The results showed that side chains induced a phase transition from colhp phase to colh phase, namely dimers T3Dn (n = 6–12) based on HAT3 exhibiting a single colhp phase, dimers T4Dn (n = 6, 7, 11, 12) based on HAT4 showing a highly ordered colhp phase in low-temperature region and a colh phase in high-temperature region, dimers T4Dn (n = 8–10) based on HAT4 displaying a single colhp phase and dimers T5Dn (n = 6–11) based on HAT5 indicating a single colh phase. Dimers T4Dn showed a phase competition between colh phase and colhp phase induced by linkages. Surprisingly, a unique phenomenon was found by us, that is, those compounds in which linkage lengths were twice those of side chains showed the largest enthalpies, the smallest intracolumnar spacings and the highest charge-carrier mobilities among their homologues, respectively, which implied that they formed the most highly ordered phase among their homologues.