A novel process for graft polymerization onto a polyethylene (PE) film using atom transfer radical polymerization (ATRP) was examined. First, a PE film irradiated with an electron beam was treated with carbon tetrabromide, thereby introducing tribromomethyl groups. The number of tribromomethyl groups introduced onto the film could be controlled by adjusting the electron beam irradiation dose. Methyl methacrylate (MMA) was then graft-polymerized by ATRP in the initiator-introduced PE film in the presence of a copper catalyst. Based on FTIR spectra from the PMMA grafted films, the behavior of graft polymerization reactions on the film surface and inside the film are discussed. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 2533-2538, 2011