Block amphiphilic copolymer, poly(sodium styrenesulfonate-block-N-vinylcarbazole) (PSSS-block-VCz), was synthesized by nitroxide-mediated "living" free radical polymerization in homogenous solution. The procedure of the synthesis of poly(sodium styrenesulfonate) (PSSS) via the same technique was modified to reduce the amount of mediator and initiator needed. Camphorsulphonic acid (CSA) and acetic anhydride (AA) were used as rate-accelerating additives in polymerization of PSSS and PSSS-block-VCz, respectively. The physicochemical and photophysical properties of PSSS-block-VCz copolymer were determined and discussed.