The atom-transfer radical polymerization of styrene was carried out in bulk at 110 degrees C with a newly synthesized bromine-containing anthracene derivative, 9,10-bis(1-bromoethylcarbalkoxymethyl)an (ANTDBr), as a bifunctional initiator and a cuprous bromide complex Cu(I)Br/2dHbipy (dHbipy = 4,4＇-di-n-heptyl-2,2＇-bipyridine). g.p.c. and n.m.r. studies revealed that the initiation efficiency of ANTDBr is 100% and the polymerization proceeds in a controlled fashion, providing low-polydispersity polystyrenes with one anthracene chromophore in the middle of the main chain. This success opens up a new route to well-defined anthracene-labelled polymers including random and/or block copolymers, which will be useful as probe polymers to study, e.g., local chain dynamics by the fluorescence depolarization technique.