This paper reports the synthesis, liquid-crystal behavior, and charge-transport properties in the mesophase of triphenylene Schiff bases and their copper(II), nickel(II), and oxovanadium(IV) complexes. The thermal and electronic properties of the Schiff bases are modulated by coordination to the corresponding metal moieties, which have the ability to self-assemble into linear structures and help the alignment of the triphenylene columns. This produces two kinds of electronically nonconnected columnar regions, one purely organic and one more inorganic. The most remarkable effect is a striking charge mobility enhancement in the metal-containing mesophases, due to the contribution of the more inorganic columns: in comparison to values of hole mobility along the columnar stacking for the purely organic columnar mesophases, on the order of 10-7 cm2 V-1 s-1, these values jump to 1-10 cm2 V-1 s-1 in these hybrid inorganic/organic columnar materials.