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 degreesC. 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 degreesC, but tBA was polymerized at 60 degreesC. Gel permeation chromatography (GPC), FTIR, NMR, UV spectroscopies, and TGA were used for the characterization of the polymers synthesized. (C) 2004 Wiley Periodicals, Inc.