Supramolecular complexes of alkali metals and their capability of electron transfer and generation of carbanions have been utilized in the polymerization of methyl methacrylate. Unusual living, metal-free polymers of methyl methacrylate, their structure, and properties are discussed. The structure of polymers and polymerization mechanism were analyzed by H-1, C-13, K-39, and C-13 DEFT (distortionless enhancement by polarization transfer) NMR spectroscopy.