Cross-linked polyacrylic resin supported-cobalt (II) catalyst was successfully employed in controlled/"living" radical polymerization of various monomers including n-butyl acrylate (BA), ethyl methacrylate (EMA) and styrene (St). Well-defined polymers with predetermined molecular weight and relatively narrow molecular weight distribution were synthesized. After polymerization, the supported cobalt (II) catalyst was easily and effectively removed from the polymerization system by simple centrifugation and very pure polymer products were obtained (Co residue < 0.1 ppm). Using the obtained polymers as macroinitiators, polymerization of methyl methacrylate (MMA) and fluorinated methacrylate ether 2-[(perfluorononenyl)oxyl] ethyl methacrylate (FNEMA) were performed, respectively. Well-defined and pure diblock copolymers PBA-b-PMMA, PS-b-PMMA and PS-b-PFNEMA were synthesized.