A new family of ligands (dual sigma - pi ligand), i.e. chelating lithium alkoxides, Li-O-(CH2-CH2O)nCH3, is shown to be very effective in promoting the living anionic Polymerization of methacrylic and acrylic esters, including a number of primary alkyl acrylates such as n-butyl acrylate and 2-ethylhexylacrylate.