Abstract: Atom transfer radical polymerization (ATRP) was carried out by using trivalent iron halide as catalyst. The trivalent iron halide was reduced by monomer to form a low-valent state iron halides and halogen-containing monomer (initiator). In the presence of a phosphorus-containing ligand, the methyl methacrylate and styrene polymerization was carried out. The effect of phosphorus ligands structure on the polymerization of methyl methacrylate (MMA) and styrene (St) was investigated. The results show that the obtained poly(methyl methacrylate) (PMMA) and polystyrene (PS) show a single gel chromatograms peak, and the molecular weight distribution is less than 1.5. The PMMA-block-PS can be prepared through sequence polymerization of methyl methacrylate and styrene.