Poly(glycidyl methacrylate) (PGMA) was synthesized by the RAFT method in the presence of 2-cyanoprop-2-yl dithiobenzoate (CPDB) chain transfer agent using different [GMA]/[CPDB] molar ratios. The living radical polymerization resulted in controlled molecular weights and narrow polydispersity indices (PDI) of approximate to 1.1. The polymerization of pentafluorostyrene (PFS) with PGMA as the macro-RAFT agent yielded narrow PDIs of <= 1.2 at 60 degrees C and <= 1.5 at 80 degrees C. The epoxy groups of the PGMA block were hydrolyzed to obtain novel amphiphilic copolymer, poly(glyceryl methacrylate)-block-poly (pentafluorostyrene) [PGMA(OH)-b-PPFS]. The PGMA epoxy group hydrolysis was confirmed by H-1 NMR and FTIR spectroscopy. DSC investigation revealed that the PGMA-b-PPFS polymer was amorphous while the PGMA(OH)-b-PPFS displayed a high degree of crystallinity.