A glycidyl azide polymer with pendent N, N-diethyl dithiocarbamate groups (GAP-DDC) was prepared by the reaction of poly(epichlorohydrin) (PECH) with pendent N, N-diethyl dithiocarbamate groups (PECH-DDC) and sodium azide (NaN3) in dimethylformamide (DMF). It was then used as a macro-photoinitiator for the graft polymerization of methyl methacrylate (MMA). Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Conversion was determined gravimetrically and first-order time conversion plot for the polymerization system showed linear increase with the polymerization time indicating that polymerization proceed in controlled fashion. The molecular weight distribution (M-w/M-n) was in the range of 1.4-1.6 during polymerization. The formation of poly(methyl methacrylate-g-glycidyl azide) (PMMA-g-GAP) graft copolymer was characterized by gel permeation chromatography, FT-IR spectroscopy, Thermogravimetric analysis, and differential scanning calorimetry. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 398-403, 2009