A novel hexafunctional discotic initiator, 2,3,6,7,11,12-hexakis(2-bromobutyryloxy)triphenylene (HBTP), was synthesized by the esterification of 2,3,6,7,11,12-hexahydroxytriphenylene with 2-bromobutyryl chloride. Atom transfer radical polymerizations of styrene, methyl acrylate, and n-butyl acrylate were carried out in 50 vol % tetrahydrofuran with HBTP/copper(I) bromide/2,2 ' -bipyridyl as an initiation system. The polymers produced had well-controlled molecular weights and narrow molecular weight distributions (<1.2). On the basis of H-1 NMR spectra of the star polymer and its hydrolyzed products, we can conclude that the initiator quantitatively initiated the polymerization of vinyl monomers and that a star polymer with a discotic core was obtained.