Thin films of four discotic liquid-crystalline hexa-peri-hexabenzocoronene (HBC) derivatives carrying three diacetylenic side chains and three saturated alkyl chains at different positions around the central HBC core were prepared on phenyltrichlorosilane-modified SiO2 substrate by the Chinese brush-coating method. The brush-coated films of molecules with D3h symmetry and C1 symmetry all exhibited anisotropic alignment with an edge-on orientation and molecular π-π stacking along the coating direction on the surface, in contrast to the spin-coated films, where a mixture of face-on and edge-on orientations was obtained. Hexagonally packed columnar structure or lamella-like columnar structure was obtained, depending on the location of the diacetylenic unit along the chain. UV irradiation of the films resulted in cross-linking/polymerization of the molecular columns. Among them, the lamella-like structure with a diacetylene unit closer to the HBC core gave more closely packed and ordered HBC arrays with the poly(ene-yne) backbones stretching along the column direction, based on a variety of experimental evidence. A thin-film transistor based on this irradiated film gave a highest mobility of 1.5 cm2 V-1 s-1 along the column direction, which is a 3 orders of magnitude improvement over that of the monomeric film. However, for those with a diacetylenic unit extended farther away from the core, cross-linking between neighboring columns was suggested to occur and no mobility can be measured for devices based on those films.