A discotic 2,6,10-trihydroxy-3,7,11-tripentyloxytriphenylene material and a triphenylene-based hyperbranched macromolecule were synthesized, in which the latter was prepared from AB m molecules in a one-pot reaction. Adipic chloride and butyryl chloride were chosen as terminal groups to the 2,6,10-trihydroxy-3,7,11-tripentyloxytriphenylene. Mesophase and their structural orders were determined using a polarized optical microscope and a differential scanning calorimeter. Carrier mobilities of the pure and composite materials were measured via a time-of-flight method. A change in carrier mobility on the morphology of the materials was further discussed. It was found that degree of crystallization was the key for a discotic triphenylene material to possess charge-transporting properties, no matter it is ordered or disordered.