Novel bifunctional initiators [1,1′-Bi-2-naphthol bis(2-bromo-2-methylpropionate); (R)-, (S)-, and racemic-] were synthesized from the esterification of 1,1′-bi-2-naphthol and used as initiators in atom transfer radical polymerization (ATRP) in conjunction with N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA), and copper (I) bromide or copper (I) chloride. The initiators synthesized were completely characterized by UV, FTIR, NMR, and Mass spectroscopies. A detailed investigation of the ATRP of methyl methacrylate (MMA) with the bifunctional initiators (BBiBN) along with CuBr or CuCl/PMDETA catalyst system in anisole was carried out at 30°. Thus, MMA polymerization is shown to proceed with first-order kinetics, with predicted molecular weight, and narrow polydispersity indices. The ATRP of glycidyl methacrylate (GMA) and tert-butyl acrylate (tBA) were also performed with BBiBN initiator in conjunction with CuBr/PMDETA catalyst system. The polymerization of GMA was carried out at 30°C, but tBA was polymerized at 60°C. Gel permeation chromatography (GPC), FTIR, NMR, UV spectroscopies, and TGA were used for the characterization of the polymers synthesized. © 2004 Wiley Periodicals, Inc.