alpha-Hydroxy and alpha,omega-dihydroxy polymers of 2-(dimethylamino)ethyl methacrylate (DMAEMA) of various molecular weights were synthesized by group transfer polymerization (GTP) in tetrahydrofuran (THF), using 1-methoxy-1-(trimethylsiloxy)-8-methyl propene (MTS) as the initiator and tetrabutylammonium bibenzoate (TBABB) as the catalyst. The hydroxyl groups were introduced by adding one 2-(trimethylsiloxy) ethyl methacrylate (TMSEMA) unit at one or at both ends of the polymer chain. The ends were converted to 2-hydroxyethyl methacrylate (HEMA) units after the polymerization by acid-catalyzed hydrolysis. Gel permeation chromatography (GPC) in THF and proton nuclear magnetic resonance (H-1-NMR) spectroscopy in CDCl3 were used to determine the molecular weight and composition of the polymers. These mono- and difunctional methacrylate polymers can be covalently Linked at the hydroxy termini to form star polymers and model networks, respectively.