The ATRP technique has been applied to a photofunctional carbazole (Cz) monomer, 2-(9-carbazolyl)ethyl methacrylate. The molecular weight and its distribution of polymers obtained were successfully controlled by polymerization time and conversion of monomers, indicating that the polymerization proceeded by the living mechanism. To introduce an energy acceptor at the chain end, a novel initiator bearing an anthracene (An) moiety was synthesized and used for the living radical polymerization. The NMR and spectroscopic analyses showed that each Cz polymer thus obtained was quantitatively labeled with An. Fluorescence spectra showed highly efficient energy migration and transfer from Cz to An. These results indicate that the ATRP method is applicable for synthesis of well-defined polymers containing various functional units.