A series of new hexaalkoxytriphenylenes having 1, 2, or even 3 lateral attached acrylate moieties as polymerizable groups were synthesized and characterized. The conditions for the photopolymerization of these monomers in thin film were evaluated and tested. The bisacrylates and trisacrylates were used to build insoluble networks. When a mask is used during the irradiation, patterned films could be prepared. The polymerization reaction was controlled by GPC and FTIR spectroscopy. The networks and patterned structure were confirmed by UV spectroscopy, surface profiles, and SEM photographs. Since hexaalkoxytriphenylenes are known as excellent photoconductors, the photopolymerized films were utilized as hole transport layers in two layered organic light-emitting diodes (LEDs) with Alq(3). The LED preparation, characterization, ana performance are described.