Poly(epichlorohydrin) (PECH) with pendent NN-diethyl dithiocarbamate groups (PECH-DDC) was prepared by reaction of PECH with sodium NN-diethyl dithiocarbamate (DDC) in anhydrous ethanol, before being used as a macrophotoinitiator for the graft polymerization of methyl methacrylate. Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Controlled radical polymerization was confirmed by the linear increase of the molecular weight of polymers with conversion. The polydispersity remained at 1.4-1.6 during polymerization. The formation of PMMA-g-PECH copolymer was characterized by GPC, H-1-NMR, FTIR spectroscopy, and DSC. (C) 2008 Wiley Periodicals, Inc.