The synthesis and characterization of diblock and triblock copolymers produced by a two-component iniferter system is reported. These materials, designed for possible water treatment applications, consist of a hydrophilic poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) block and a very low surface energy poly(1,1'-dihydroperfluorooctyl methacrylate) (PFOMA) or poly(1,1,2,2-tetrahydroperfluorooctyl acrylate) (PTAN) block. Angle-dependent X-ray spectroscopy results and water contact angle measurements indicate that the surfaces of PDMAEMA-b-PFOMA diblock copolymers consist primarily of PFOMA. Transmission electron microscopy reveals that the block copolymers are microphase-separated, exhibiting either cylindrical or layered morphologies that do not change appreciably upon exposure to water. Both water uptake and water flux increase with increasing PDMAEMA content.