The living radical polymerization of 4-acetoxystyrene via the RAFT process has been achieved employing bulk, solution and emulsion techniques. The rate of polymerization was stated between 60 degreesC and 90 degreesC. Increasing the temperature increases the rate of polymerization without affecting the polydispersity. Poly(4-acetoxystyrene) with narrow polydispersity (1.08) Was obtained. Various novel dithiocarboxylic esters and dithiocarbamates were screened as chain-transfer agents for the RAFT polymerization of 4-acetoxystyrene. The block copolymerization of poly(4-acetoxystyrene) with to poly(4-acetoxystyrene)-block polystyrene confirmed the presence of active chant ends in the first block. The acetoxy polymers were hydrolyzed to the corresponding hydroxy polymers under mild basic conditions.