Polymerisation of methyl methacrylate was conducted by using alkyl lithium/dimethylsulfoxide (DMSO) system as initiator in toluene. A special attention was focused on using some lithium polyetheralkoxides as polymerisation promoters at ambient temperatures. Poly(methyl methacrylate) samples were characterized with Gel Permeation Chromatography (GPC), Nuclear Magnetic Resonance Spectroscopy (H-1 NMR) and Differential Scanning Calorimetry (DSC). The positive effect of the mu/sigma type ligands such as lithium 2-(2-methoxyethoxy)ethoxide (LiOEEM), 2-(methoxy)ethoxide (LiOEM) on controlling the living character, molecular weight, stereo regularity and the yield of the produced polymers was demonstrated. It has been found that this approach provided high polymerisation yields and low polydispersity but low initiator efficiency.