Palladium-catalyzed cross-coupling between 3,4-dialkoxyphenylboronic acids (1a-d) and 2,3,6,7,10,11-hexabromotriphenylene (2) provided 2,3,6,7,10,11-hexakis[3,4-bis(alkoxy)phenyl]triphenylenes, C18H6[C6H3(OC(n)H(2n + 1)2]6 where n = 6, 8, 10, and 12 (3a-d). Cyclodehydrogenation of the aryl-substituted triphenylenes 3a-d using ferric chloride oxidation followed by methanol reduction produced 6,6',6'',7,7',7'',10,10',10'',11,11',11''-dodecaalkoxy-2,3':3,2':2',3''- tris(triphenylenylene)s, C54H18(OC(n)H(2n + 1))12 where n = 6, 8, 10, and 12 (4a-d). The mesomorphic properties of the compounds 3a-d and 4a-d were investigated by differential scanning calorimetry (DSC) measurements, polarizing microscopy, and wide angle X-ray diffraction (WAXD). The triphenylenes 3a-d exhibited a columnar mesophase in the range of 111-126, 85-104, 74-103, and 47-101 °C, respectively. Upon oxidation of the moiety, the columnar mesophases shift to higher temperatures and exist in a much broader range of temperatures: for the tris(triphenylenylene)s 4a-d, they have been observed in the range of 180-430, 150-370, 120-322, and 104-306 °C, respectively. Finally, the self-assembly at the interface between a solution of 4c and a graphite substrate has been studied by scanning tunneling microscopy. Molecularly resolved imaging revealed a highly ordered monolayer exhibiting a two-dimensional hexagonal lattice.