sBuLi and tBuLi have been combined with a new family of ligands, i.e. lithium silanolates, and used as initiators for the ligated anionic polymerization (LAP) of methyl methacrylate (MMA) in toluene at 0 degrees C. Compared to other known mu-ligands, the accordingly formed Bu(Me-2)SiOLi are more efficient stabilizers for the active centers. Under appropriate reaction conditions, a fast polymerization proceeds quantitatively without self-termination at 0 degrees C and leads to high molecular weight polymer of narrow molecular weight distribution (<(M)over bar(w)>/<(M)over bar(n)> < 1.2) and high isotacticity (90% isotactic triads).