Poly(1,1-dihydroperfluorooctyl acrylate) (PFOA) based block copolymers were synthesized for use as lipophilic/"CO2-philic" surfactants for carbon dioxide applications. The first step was the synthesis of telechelic polystyrenes capped with the N,N-diethyldithiocarbamate group (TD-PS) using the iniferter method. The functionalities of the telechelic polystyrene samples were analyzed by UV/vis, H-1 NMR, and three-dimensional GPC. The 3-D GPC analysis provided detailed information on the percent functionality of end groups across the molar mass distribution. The results showed that the functionality was constant for different chain lengths. Block copolymers were synthesized by subsequent polymerization of FOA using telechelic polystyrene as a macroinitiator. The chemical composition, the glass transition temperatures, and the solubility of the block copolymers were studied.