A new catalytic system for the ATRP polymerization of styrene and methyl methacrylate (MMA) based on neodymium(II) iodide, 2,2'-bipyridyl, and 1-bromo-1-phenylethane was investigated. The polymer was isolated at a conversion of 18.4 wt%. The secondary polymerization initiated by the neodymium(II) iodide-based system was carried out to verify the proposed mechanism of polymerization. The starting polymer was prepared at 110°C in the presence of the NdI2-Bipy-BPE system. The secondary polymerization stopped when a monomer conversion of 14.2wt% was attained. It was observed that the catalytic system based on neodymium(II) iodide developed is a new agent pseudo-living radical polymerization.